Sri Lankan trio Mahela Jayawardene, Kumar Sangakkara and Muttiah Muralitharan and former India players Sunil Gavaskar and Sourav Ganguly will also be making appearances.
Former England great Botham starts his walk on Friday in Kilinochchi in the north of the country and will cover 160km in eight days before finishing at the Seenigama cricket ground in the south.
"Beating the oppressive heat and humidity will be testing but I look forward to the challenge," the 57-year-old told a news conference on Thursday. "I love a challenge."
'Beefy's Big Sri Lanka Walk 2013' will raise funds for those affected by the 30-year war in the country and for projects operated by the Foundation of Goodness in Sri Lanka with the support of the Laureus Sport for Good Foundation.
Botham has been walking for charity since 1985 when he first pledged to raise millions of pounds to help people suffering from blood cancers.
He visited Sri Lanka in 2005 soon after the Asian tsunami and played a key role in the establishment of the Foundation for Goodness project.
Botham was back in the country in 2009 to oversee the launch of a sports centre in Seenigama that was hit by the tsunami.
In 2011 he made another visit for the opening of a similar sports complex in the north of Sri Lanka.
Botham is one of the greatest cricketing all-rounders of all time. He won 102 test caps, hitting 14 centuries and taking 383 wickets.
(Editing by Tony Jimenez)
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