In Monday's second match in Group B, defending champion Novak Djokovic saw off a determined challenge from Russian Nikolay Davydenko to register a three sets victory.
Meanwhile, Ferrer's victory ensured he joins defending champion Roger Federer -- who has qualified from Group B -- in the last four of the competition.
McCann, who claimed a bronze medal in the World B Championship road race in Switzerland during the summer, finished 52 seconds ahead of Irish time trial champion David O'Loughlin in the 40K event.