The seven-strong team left from the Capital on Monday and will visit Belfast, Dublin and Bristol in their mission on behalf of the Meningitis Research Fund (MRF).
The party – which includes an “overweight electrician” and a civil servant who has not mounted a bike for 40 years – will cover 500 miles and hope to raise thousands of pounds.
The cycle coincides with Meningitis Awareness Week.
One participant, Chris Wilson, is taking part for his daughter, Sophie, who survived the illness in 2009 at the age of 17.
He said: “She survived, having had an early diagnosis and treatment.
“However, many more are less fortunate.
“We kicked off the challenge in Edinburgh to highlight the MRF’s Counting the Cost of Meningitis campaign.”