The tie-up features a joint digital marketing programme, called UK Inspiration, which features American Express offering travel information and deals to its card members worldwide, through a dedicated website, amexnetwork.co.uk/ukinspiration.
The site gives American Express users exclusive travel offers alongside "insider information" from a selected group of UK fashion, food, entertainment and travel bloggers.
VisitBritain will ensure that the destination content, images and blogs on the site are kept up to date.
The partnership will be jointly promoted by the two brands, featuring PR, social media and activity at American Express foreign exchange outlets.
The UK Inspiration activity will run under VisitBritain's "You're invited" banner, feeding into the £100m global marketing campaign due to launch later this month.
The Government is contributing £50m in funding to help the tourism body bring four million overseas visitors to the UK and increase tourism spend by £2bn.
Laurence Bresh, director of marketing, VisitBritain, said: "We’re delighted to be working with American Express. This partnership gives us the opportunity to showcase Britain and to present ideas and offers which encourage potential visitors to travel now.
"Partner marketing deals such as these are key to providing an international platform for tourism destinations and businesses across Britain."
American Express will join British Airways, Lastminute.com, ferry companies P&O and DFDS,hotel chain Radisson Edwardian and budget airline easyJet, among other travel brands, as a founding partner for the marketing drive.