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The Princesses in general
- Blonde, Brunette, Redhead: Blair is blonde, Hadley and Isla are brunettes, and Delancy has blonde hair with a very slight red undertone.
- Color-Coded for Your Convenience: Pink for Blair, blue for Hadley, indigo for Isla, and purple for Delancy.
- Damsel out of Distress: They manage to escape the room with their smarts, patience and technology.
- Five-Token Band: Blair and Delancy are white, Isla is Japanese, and Hadley is Latina.
Blair Willows
Blair Willows/Princess Sophia of Gardania
- Voiced by: Diana Kaarina
The main protagonist of the movie, Blair is an orphan who doesn't know a thing about her past. As an adult, she works as a waitress until she wins the lottery and attends Princess Charm School, a boarding school for princesses. In reality, she's the lost princess Sophia of Gardania, and the only survivor of the royal family, and had to follow clues to discover her true identity.
- Cool Big Sis: To Emily.
- Changeling Fantasy: Blair was adopted by her poor foster mother, became a waitress, then enter the titular school as a Lady Royal. The ending reveal Blair was Sophia, the lost princess and heir to the throne, all along.
- Cute Clumsy Girl: Blair is teased and humiliated relentlessly for it.
- Doorstep Baby: Was found on the doorstep of Ms. Willow's apartment as an infant. Naturally, the exact same happened to the baby Sophia of the Royal Family, and all this information concludes Blair is indeed the same baby Sophia.
- Expy: Of Princess Rosella from Barbie as the Island Princess both the protagonists are the lost princesses in same ways.
- Happily Adopted: Blair embraces her family when she was crowned Princess. She loves her family so much she is willing to go to Princess Charm School just for the money needed for her mother and sister. Her little sister Emily is also adopted as stated by Blair when opening Emily's care package.
- Letting Her Hair Down: When Blair is introduced, she has her hair in a Prim and Proper Bun. When she changes into her school uniform, her hair falls, but has a small ponytail left on the side. When she is revealed to be Princess Sophia near the end, her hair falls entirely loose with wavy curls.
- Pink Means Feminine: A given with someone played by Barbie.
- Princesses Prefer Pink: Blair's fancy dress is pink. Her Custom Uniform is of that color too; and regular uniforms include pink skirts and pumps.
- Percussive Maintenance: How Blair makes her old TV work.
- Really Royalty Reveal: The second half of the movie has Blair suspect she's the baby Sophia of the Royal Family, who didn't die in the car accident and found on someone's doorstep and is the true heir to the throne. However, only the crown will confirm this — it shining when atop Blair's head confirms she is indeed the rightful owner.
- Significant Birth Date: The day she claims to be her birthday, April 26th, which was also the day Ms. Willows found her on her doorstep, was the day the Royal Family of Gardania died in the car crash.
- Spanner in the Works: Blair being picked in the PCS lottery (thanks to Emily entering her name in) proceeded to throw Devin's entire plan off the rails, and she resorts to increasingly blatant methods of getting Blair out of the way; this simply makes everyone more suspicious of her actions.
- Strong Family Resemblance: She looks exactly like her birth mother, Queen Isabella. This is what makes her, Hadley, and Isla realize that she's the lost princess.
- Walking Spoiler: She's the baby Sophia of the Royal Family, and the true heir to the throne.
Isla
Princess Isla Kokoro of Japan
- Voiced by: Shannon Chan-Kent
- Big Damn Hero: The girls escaping the saferoom was ultimately due to her. She heard Dame Devin change the password, and recognized the melody from somewhere, as she had been singing it in her head recently, and she told Blair which numbers to click to unlock the door.
- Shrinking Violet: Isla is initially shy, especially when it comes to people hearing her music.
- Motifs: Musical notes are associated with her. Her laptop has a note on it, and (at least in the book) she has a treble clef attached to her ballgown.
- Token Minority: She fills the "Asian" slot.
- True Blue Femininity: She wears an indigo ballgown and her second uniform is indigo.
- Toyless Toyline Character: She didn't get a doll; her role was originally intended for Delancy.
Hadley
Princess Hadley Ainsley
- Voiced by: Ali Liebert
- Chekhov's Skill: Hadley's ability in sports allows her to cross the Laser Hallway quickly.
- Latino Is Brown: She has a tan and brown hair.
- Tomboy Princess: She loves soccer, and is skilled at gymnastics.
- True Blue Femininity: She wears a blue ballgown and both of her uniforms are blue.
Delancy
Lady Royal Delancy Devin
- Voiced by: Brittney Wilson
- Alpha Bitch: She picks on Blair and tries to make it clear she doesn't belong at charm school.
- Book on the Head: Delancy manage to walk with about twenty books.
- Easily Forgiven: Delancy is forgiven for her hostile attitude and is crowned Blair's Lady Royal.
- Expository Hairstyle Change: Delancy wears her hair in an elaborate updo like her mother's but lets it down for the coronation. As she is on Blair's side at this time, the new hair represents Delancy getting off the path Dame Devin has laid out for her.
- Expy: Delancy is akin to Princess Luciana, being a purple-clad princess who is a pawn in her mother's scheming. However, Delancy is significantly bitchier than Luciana was, and furthermore is something of an active participant in her mom's schemes, at least until Blair getting thrown out and mounting evidence makes her begin her Heel–Face Turn.
- Graceful Ladies Like Purple: Her ballgown and second uniform is purple.
- Heel–Face Turn: Delancy was never "evil" so much as "mean". As soon she learns there's a chance Blair is the legitimate heir to the throne, she decides to help uncover the truth.
- Lovable Alpha Bitch: During the last part, after the Heel–Face Turn above. As Blair stated, she could never prove she was Princess Sophia without Delancy's help.
- Walking Spoiler: She's not the true heir to the throne; Blair is.
Allies and sidekicks
Headmistress Privet
Headmistress Alexandra Privet
- Voiced by: Morwenna Banks
- I Am Very British: She speaks with a posh accent.
- Proper Lady: She is very reserved.
- Reasonable Authority Figure: To Blair. She helps tutor her to learn the ways of royalty properly and is accepting of her once she is revealed to be Princess Sophia.
- Red Oni, Blue Oni: The blue to Dame Devin's red.
- Stern Teacher: She can be this at times.
- True Blue Femininity: She wears a blue suit.
Prince Nicholas
A prince from Prince Charming Academy, and Blair's possible boyfriend.
- Adorkable: The entire dance class scene is proof enough.
- Satellite Love Interest: Nicholas is this for Blair.
- Ship Tease: With Blair.
Prince
- Big Friendly Dog: He's a Golden retriever. It comes with the territory.
- Hair of Gold, Heart of Gold: Well, fur of gold, but same idea.
- Non-Human Sidekick: He's this to Blair and company, as well as her family.
Grace, Caprice, and Harmony
Miranda
Princess Miranda of Philadelphia
- Voiced by: Miranda Ram-Nolte
- The Danza: She was named after her voice actress, who died shortly after the movie was released.
- True Blue Femininity: She wears a dark blue ballgown.
Portia
Princess Portia of Narcissia
- Voiced by: Ali Liebert
- Beta Bitch: She's Delancy's right hand girl, but not interested in putting any princesses "in their place" like her friend is.
- Cloudcuckoolander: Two words: Floor cakes.
- Innocent Beta Bitch: Due to being ditzy, and not very bitchy.
- Redheads Are Uncool: She is a ginger who is depicted as kind of crazy.
Josette and Lorraine
- Genki Girl: They are both cheerleaders who can't stop doing their routine in random places, and get very excited when talking about parties.
- Those Two Girls: They are always seen together.
- Token Minority: Josette is black.
Antagonists
Dame Devin
- Voiced by: Nicole Oliver
- Abusive Parents: Dame Devin is a borderline example, calling her daughter a "useless child". Dame Devin seems to be so domineering over her daughter that Delancy has no choice but to do what she says. It's hinted that Dame Devin wants to live her dream as a princess through her daughter and use her to rule Gardania from the shadows.
- Complexity Addiction: Dame Devin didn’t have to arrange ways Blair to leave the school like accusing her of stealing and raising the fire alarm. She should’ve just let her be a Lady Royal (that was all that Blair wanted), and found subtle ways to ensure Blair didn’t learn the truth, such as her being an Identical Stranger. Because of Dame Devin’s actions, Delancy and Blair became suspicious.
- Didn't See That Coming: She murdered the Royal Family of Gardania in a car crash so Delancy could take their place once she's older. However, she didn't know the baby Sophia survived the accident and was left on Ms. Willows' doorstep, meaning she now has stiff competition for the throne.
- Everyone Has Standards: Of a sort; when she sees Portia simply spinning around holding a book above her head during posture class, Devin simply tells her "You're doing fine". She knows trying to instruct Portia isn't worth the energy.
- Evil Teacher: She's the villain.
- Expy: Of Queen Ariana; both are main villains who tried to taking over the kingdoms through their families.
- Near-Villain Victory: Dame Devin comes within two seconds of having her daughter crowned, but Blair arrives last-minute to reclaim it.
- Never Say "Die": Dame Devin exclaims on live television that she "eliminated" her own sister-in-law .
- Only One Name: Sort of, considering "Dame" is a title, not an actual name. We never learn her actual first name.
- Red Oni, Blue Oni: The red to Headmistress Privet's blue.
- Stunned Silence: The instant Dame Devin gets a good look at Blair's face for the first time, she stares in shock. Later revealed to be because she noticed the resemblance to the late Queen Isabella and the possibility that Blair is the lost princess Sophia.
- Vile Villain, Saccharine Show: Dame Devin, for being one of the few characters in a Barbie movie to have actually murdered someone.
- We Will Meet Again: As the guards drag her out of the ballroom after she accidentally confessed about her involvement in the car crash, she yells in protest that Delancy should be crowned, before swearing revenge.Dame Devin: No! You can't do this to me! Get your hands off me! You have to crown Delancy! You have to! You'll pay for this!