The "Grand Depart" opening stage on September 7 will send riders on 10 laps of a 13-kilometre circuit, starting and finishing on The Strand in the city centre, close to the Royal Liver Building.
Liverpool has featured in the 2006, 2007 and 2008 tours, but has never previously been the launch point for the eight-day race.
"The opening circuit will be perfectly suited to the sprinters, and whoever wins stage one will pull on the first yellow jersey of 2014," said race director Mick Bennett.
Liverpool's assistant mayor, councillor Wendy Simon, added: "This is a huge coup for the city. This race attracts some of the best riders from across the globe with previous races featuring elite cyclists such as Bradley Wiggins, Mark Cavendish and Chris Froome. There's a real momentum building for cycling in this city."