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Arc Rise Fantasia
Given the hard nature of these boss fights, just coming on top of them is enough of an awesome moment as it is relief.
Players are likely to feel especially ecstatic at beating one of the many tough optional bosses, especially the optional Rogress Mashgar, Kudoan and Allul.
Anytime your character learns a new Excel Act. Especially one that does Area of Effect damage and kill all enemies in one shot.
Special Mention goes to Niko: His first two Excel Acts consisted of a Single Target attack and a self-full heal. All the sudden he gets Niko Cannon and literally blows the enemy to smithereens!
It gets even better when he learns Trickster.
Absin: Witness the Logos of Judgment... and judge you I will!
The entire game's soundtrack.
A small one for Ryfia: Early in the game when the party is speaking with Prince Wiess, Ryfia talks back to him, and he responds by throwing a dagger that barely misses her head. She doesn't even blink.