Napoleon Solo is Number 1 of Section II, U.N.C.L.E.'s Chief Enforcement Agent. Served as a soldier during The Korean War before joining U.N.C.L.E.. Napoleon is a serial womanizer, and often ends up with a new girl during or at the end of the episode.
- "Awesome McCool" Name: Provided by Ian Fleming, who gave it to a minor character in the James Bond novel Goldfinger.
- Badass in a Nice Suit: Is nearly always wearing suits, with the occasional tux thrown in.
- The Casanova: And a shameless flirt.
- The Charmer
- Chick Magnet
- Chivalrous Pervert
- Dating Catwoman: With Angelique from THRUSH. The other women usually defect before hooking up with him.
- The Nicknamer: Tends to throw these out at Illya, for example calling him "I.K." or "Tovarishch." He doesn't tend to do it consistently or repeat names.
Illya Kuryakin is Number 2, Section II in U.N.C.L.E.. He is on loan from the USSR, and is shown to be an active member of the Soviet military.
- Badass Bookworm: He has a Masters degree from the Sorbonne and a PhD in quantum physics from Cambridge and is often shown to be working in the U.N.C.L.E. labs between field assignments.
- The Cast Show Off: David McCallum is an accomplished musician. In the second season episode "The Ultimate Computer Affair", Illya goes undercover as very disreputable busker to get himself thrown into a THRUSH prison. And in the third season episode "The Take Me to Your Leader Affair", he plays guitar and sings a duet with the "Innocent of the Week" played by Nancy Sinatra on the flimsiest of "creating a diversion" pretexts. McCallum also wrote the song that he and Nancy Sinatra sang.
- Celibate Hero: although he has his romantic moments, Illya is more likely to be caustic and dismissive to women who show attraction to him, and a lot of the female guest stars do. He is a Chick Magnet almost in the same league as his Casanova partner.
- Deadpan Snarker: Even more likely to pull out snark than Napoleon.
- Dirty Communists: Subverted, Illya was one of the first positive portrayals of a Soviet on US television.
- Master of Disguise: He even goes undercover as a yeti once.
- Mr. Fanservice: McCallum was hugely popular in the 1960s.
Mr. Waverly is Number 1, Section 1 at the New York U.N.C.L.E. headquarters.
- Badass in Charge: When Waverly steps out of his office, THRUSH villains beware! And his own men sometimes need to watch out because he's quite prepared to knock them unconscious to add verisimilitude to his undercover performances.
- Da Chief
- The Casanova: Steals the woman from Napoleon at the end of the episode twice.
- The Spymaster: As the head of U.N.C.L.E. New York and one of the five heads of the entire organization, Mr. Waverly's reach goes far. Also seen in his plan in "The Waverly Ring Affair."
- Retired Badass: Though retired from fieldwork, Mr. Waverly sometimes comes out to backup his agents. We also get hints at his past career from his interactions with the older THRUSH agents he runs into.