Three times as many of London's workers as the national average - 16% - took more than an hour.
Most people - 71% - drove to work, with 10% walking, 7% catching a bus, 5% getting a train and 3% cycling.
The picture was very different in the capital, with only 35% of those who worked in London driving to work and around half of all workers taking public transport (20% train, 18% Underground and 12% bus).
Outside London, only 9% of workers took any form of public transport to work. Three in five (59%) of all workers in the UK worked and lived in the same local authority district.
Commenting on the figures for commute times TUC general secretary Brendan Barber said: "The link between long commute times and high earnings suggests that transport costs are a huge barrier to people looking for work outside their local area. "With the availability of work varying greatly across the country, transport costs must be a more important factor for employment schemes.
"These figures also show that while workers in and around London are put under extreme pressure with lengthy commutes and rising transport fares, petrol prices are what matters most outside the capital, where more than seven in ten people drive to work.
"More investment is needed to encourage greater use of public transport outside London, while smarter working patterns, such as allowing people to vary start times or to work from home, would benefit workers and businesses throughout the country."
