Hughes was educated at the private Notting Hill & Ealing High School, in Ealing. She won a scholarship to read Ancient and Modern History at St Hilda's College, University of Oxford, achieving a 1. After graduating she travelled through Eastern Europe and Central Asia.
Hughes' father is the actor Peter Hughes and her brother is the cricketer and journalist Simon Hughes. Her husband is Adrian Evans, the producer of Archaos in the UK and the director of the South Bank Thames Festival. They have two children.