Pooley made a return to competitive cycling in October 2015 when she competed at the Chrono des Nations time trial, where she finished sixth. In December 2015 she announced that she would aim to compete for Team GB in the 2016 Summer Olympics in Rio de Janeiro after being approached by British Cycling's technical director Shane Sutton, who had studied the Olympic road racing courses and felt that Pooley would have a good chance of winning a medal in the time trial and of helping Lizzie Armitstead to win the road race. She also confirmed that she would continue to compete in triathlon and duathlon competitions in 2016. Pooley made her first appearance in a mass start road race for two years in April 2016 for the British national team at the Women's Tour de Yorkshire, where she helped teammate Alice Barnes to fourth place. In June 2016 announced that Pooley had rejoined the team for the remainder of the 2016 season, and that she would be part of the team's squad for the 2016 Giro d'Italia Femminile with a role as a domestique for Claudia Lichtenberg. At the Olympics, Pooley rode in the service of Armitstead in the road race, whilst in the time trial she finished 14th, just over two minutes down on winner Kristen Armstrong.