Perey was born in 1909 in Villemomble, France, just outside Paris where the Curie's Radium Institute was located. Although she hoped to study medicine, the death of her father left the family in financial difficulties.
Perey earned a chemistry diploma from Paris Technical School of Womens Education in 1929; while not a "degree", it did qualify her to work as a chemistry technician. In 1929 at the age of 19, Perey interviewed for a role as a personal assistant (technician) to Marie Curie at Curie's Radium Institute in Paris, France, and was hired. Marie Curie took on a mentoring role to Perey, taking her on as her personal assistant.