- "...if you were as generous as the old Romans, you would lend him to me for a little while..."
- — Angelica Schuyler to Eliza Schuyler about Alexander Hamilton in a letter.
Angelica's first singing role is in the "The Schuyler Sisters", where her sisters Eliza, Peggy and she sing about the revolution happening in New York. Later, she and her sisters attend a ball proposed by her father, Philip Schuyler ("A Winter's Ball"), in which she meets multiple revolutionary allies, including Alexander Hamilton. Eliza emerges with immediate feelings for Alexander upon sight, but does not approach him; Angelica strikes a conversation with him in turn and is attracted to him both by looks and demeanor. Angelica then realizes her sister's extent of feelings for Hamilton ("Helpless") and hides her own allure to him for the sake of her sister ("Satisfied"). As being a loyal and loving sister, Angelica attends and toasts Eliza's wedding to Alexander Hamilton, singing of how she will never be satisfied but is happy for her sister.
While Hamilton works at home, Angelica tells Hamilton to convince Jefferson that his new financial plan will work, so that the Congress will accept it and put the plan to action. She also informs him that she will arrive at New York to travel upstate to her father's home in Albany ("Take A Break"). During this time, she and Eliza try to convince Alexander to accompany them on vacation to Albany. Alexander refuses, saying that he has to keep improving his plan for Congress, and the sisters travel upstate without him.
During his time alone, Alexander Hamilton has an affair with Maria Reynolds ("Say No To This"), and to keep the affair secret is forced to pay her husband, James Reynolds, an amount of money. Meanwhile, Aaron Burr, Thomas Jefferson, and James Madison recollect on how lucky he is that George Washington always happens to support him ("Washington On Your Side"). Alexander is afraid they will demise of his reputation and openly writes about his affair to save himself ("The Reynolds Pamphlet"), meanwhile thoroughly bringing down and shaming his wife. Angelica comes from London when she heard about the affair. Hamilton is relieved, thinking that she has come to help redeem him, but Angelica replies that she did not come for him and stands by her sister's side. In the song Congratulations ( Cut from the musical, set in between The Reynolds Pamphlet, and Burn) Angelica yells at Alexander stating how idiotic his actions were, and that "Jefferson can do what he wants because he doesn't dignify school-yard taunts with a response." As Alexander tries to defend his action, Angelica gets overwhelmed with emotion and speaks of her loveless marriage, and how she lived to read his letters. Angelica leaves him after telling him Eliza is the best thing in both of their lives.
After Hamilton's death in a duel against Aaron Burr, Angelica returns with her sister. She supports her sister for the rest of her years, and Eliza sings about her reliance on her older sister until Angelica's death in 1814 ("Who Lives, Who Dies, Who Tells Your Story"), after which she is buried in Trinity Church near Alexander.
- Angelica serves as the "main character" of the trio of Schuyler sisters, the "oldest and the wittiest" to quote Hamilton.
- In reality, there were thirteen Schuyler siblings, only three of which were portrayed in the musical. However, only eight of the thirteen survived to adulthood.
- In the musical, Angelica sings that her father, General Philip J. Schuyler had no sons, whereas he had several sons, although the only ones who survived to adulthood were John Bradstreet Schuyler, Philip Jeremiah Schuyler, and Rensselaer Schuyler.
- Angelica Schuyler Church and her British-born, Member of Parliament husband, John Barker Church, succeeded in a plot to free the Marquis de Lafayette from his Austrian captors during the War of the First Coalition, in which other European nations tried to defeat the new First French Republic formed after the French Revolution. Despite the successful escape, the Marquis was quickly recaptured after he got lost.
- There is no textual evidence that Angelica actually 'loved' Alexander. Although they maintained a flirtatious relationship, evidence shows it was merely platonic/intellectual.
- Angelica was married before Eliza, having eloped with John Barker Church.