She began swimming at the age of four, but started rowing at her school's boat club in 2002 after a friend suggested that she would be a good cox due to her small height. de Toledo coxed Great Britain to a bronze medal at the 2005 World Rowing Junior Championships. Afterwards she took a one-year hiatus to retake A-level examinations, before going toOxford Brookes University to study psychology. de Toledo was the cox at the university for one year before joining the Leander Club in 2007. In her first full season in 2008, she secured a medal in the Ladies' Challenge Plate at Henley Royal Regatta. de Toledo graduated from the university the following year. At the 2009 World Rowing Under-23 Championships she coxed the Great Britain squad to a gold medal. It marked the first time a women's rowing team from Great Britain had won a gold medal in rowing in any age group. de Toledo returned to Oxford to study for a master's degree in psychological research at the University of Oxford in 2010. She became involved in the university's boat club, and coxed the reserve team to victory in The Boat Race 2010. de Toledo returned to the university to study a master's degree in criminology and criminal justice. She was selected by the university to participate in The Boat Race 2012. In the event, de Toledo was warned by umpires for steering too closely to the rival Cambridge squad. It came after protester Trenton Oldfield jumped into the water and protested against elitism and inequality in British society. She later was criticised for her actions. The experience meant de Toledo suffered from a lack of confidence and credited bow Alex Woods for helping her restore her interest in rowing. She trained with Team GB at Caversham Lakes after clinching a bronze medal at the European Rowing Championships. de Toledo later went through a divorce, and was left homeless when a fire destroyed her Hambleden home in 2014. She coxed the Great Britain eight rowing squad which performed strongly in the World Rowing Championships and the World Cup Regattas. de Toledo coxed the Great Britain women's eight team to win a gold medal at 2016 European Rowing Championships and finished less than one second behind the United States in Lucerne. She helped Great Britain win their first medal in the women's eight category at the 2016 Summer Olympics in Rio de Janeiro. Since retiring from rowing, de Toledo has taken up a place to study medicine at the University of Oxford. In 2017 she was found to have a benign brain tumour, which was surgically removed in March 2018.
