- After learning that another actress in the Actors' Equity Association had the name Lily Thomson, she choose the stage surname of James to honour the memory of her father, James Thomson, who had died a few years earlier.
- She is a mezzo-soprano.
- Graduated from the Guildhall School of Music and Drama, in London, England, with a bachelor of arts honors degree in acting in 2010.
- Her grandmother Helen Horton provided the voice of "Mother," the Nostromo space tug's computer in Ridley Scott's Alien (1979).
- Is a distant relative to her Mamma Mia! Here We Go Again (2018) co-star Meryl Streep. Although the two actresses don't share a scene together, James played a younger version of Streep's character.
- She is a sixth cousin of U.S. President George Bush through her American grandmother. Lily's four-times-great-grandfather, Stephen Horton, was the brother of the president's four-times-great-grandmother, Sarah Horton (their parents were Comfort Horton and Joanna Wood). Lily is thus a sixth cousin, once removed, of the president's sons, President George W. Bush and Governor Jeb Bush.
- She is the daughter of Ninette V. A. (Mantle) and James Stewart Thomson. Her father was born in Chicago, Illinois, to a Scottish father, James Hamish Thomson, from Inverkeithing, Fife, and an American mother, Helen Horton, who lived in England with Lily's grandfather. Lily's mother was born in Wegberg, Germany, to an English father, William Eric Mantle, who was a Christian minister, and a French mother, Marinette R. Touzet.
- Counts True Romance (1993) as one of her favorite films.
- Graduated from the Arts Educational School, Tring Park, in Hertfordshire, England, in 2008. In sixth form, she studied the musical theatre course curriculum and was elected head girl of the school.
- She originally auditioned for the role of Anastasia Tremaine, one of the stepsisters, in Cinderella (2015) before being cast in the the title role.
- She was in a relationship with actor Matt Smith from 2014 to late 2019.
- She has the same birthday (not the same year of birth) as her on-screen mother in Cinderella (2015), Hayley Atwell.
- The only time she has acted out giving birth in a movie was in Mamma Mia! Here We Go Again (2018). She has also acted out giving birth in the miniseries Pam & Tommy (2022).
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