The 7 Rings singer performed the iconic ballad I Won't Say I'm in Love from the 1997 cartoon hit Hercules on Thursday night.
The song was sung by Meg in the film, and Grande wore a purple dress and had her hair up in a ponytail to pay homage to the character, who is Hercules' love interest.
Grande, 26, didn't just sing lead vocals - she also played all five Muses and her back-up harmonies were pitch-perfect throughout.
The singer had been teasing her appearance on the singalong for the past week, sharing a black and white shot of Meg, while her performance was hinted at in ABC's trailer for the show.
Hosted by Ryan Seacrest, The Disney Family Singalong was an hour-long TV special broadcast on ABC and featured a star-studded line-up of celebrities and performers singing a whole host of Disney classics.
The event brought attention to the Feeding America charity, which is working to fight hunger amid the coronavirus crisis.
Christina Aguilera sang Can You Feel the Love Tonight from The Lion King, Michael Buble and Demi Lovato belted out A Dream Is A Wish Your Heart Makes from Cinderella and Josh Groban performed You've Got A Friend in Me from Toy Story.
Beyonce also made a surprise appearance to perform a cover of When You Wish Upon a Star from the 1940 classic Pinocchio, while the cast of High School Musical to sing We're All in This Together.
This wasn't the first time that Grande has tackled a Disney song - land it seems Hercules is one of her favourite movies.
In 2018, she recorded Zero to Hero for the covers album We Love Disney and she's previously explained that she loves music by the film's composer, Alan Menken.