The eight-day trek is the first expedition organised by the Westminster Challenge - a voluntary group set up last year to bridge the information gap between politicians and charities.
Politicians who sign up to expeditions regularly meet representatives from the group's adopted charities to learn more about their work. The aim is for them eventually to become parliamentary ambassadors for one or more of the causes.
The five MPs taking part in the first expedition are Ed Vaizey, the shadow arts minister, Nick Clegg, home affairs spokesman for the Liberal Democrats, Emily Thornberry, Labour MP for Islington South and Finsbury, Jenny Willott, Liberal Democrat MP for Cardiff Central, and Tobias Ellwood, Conservative MP for Bournemouth East.
The team, which will be followed by an ITV film crew, hopes to raise £150,000.