The Surrey captain has taken a lead from the feats of Ian Botham with plans to walk from John O'Groats to Dover, covering a marathon distance each day.
But he will then row from the English port to Calais, cycle to Gibraltar and take to a boat again for the final leg of the trip to Tangiers - a grand total of over 1,500 miles.
Money raised from the trip will all go to the Ben Hollioake Memorial Fund, set up to help children with terminal illnesses.
"I must be mad but I'll give it a go and try and have fun on the way," Hollioake said.
The former England one-day skipper will set out on the trip in October 2003 and expects it to take three months.
Hollioake's plans could be altered if he gains a recall to the England side - he is currently on stand-by should Andrew Flintoff fail to prove his fitness for the one-day VB Series.
But Hollioake said that the death of his brother had given him a new outlook on life, and that he was unworried by his international prospects.
"It's just a game now," he said.
"If I get picked then great but if not then I'll just take it as it comes."
The trek is just one part of the fund-raising programme, which will also include an international all-star match at The Oval on 18 July.
Ben Hollioake died tragically in a car crash in the Australian city of Perth last March.