He stood as the SNP candidate in the 1962 West Lothian by-election against Tam Dalyell polling very well and managing to some second in a seat where previously the SNP had made little impact. He became aware of the need for greater professionalism in the organisation of the SNP and diverted his attentions to this matter thereafter.
In 1969 he replaced Arthur Donaldson as SNP National Convenor, and it was during Wolfe's period as leader that the party had it's greatest electoral sucess to the Westminster parliament, winning 11 seats in the October '74 General Election. It is also Wolfe that is credited with doing much to develop the SNP as a clearly defined left-of-centre political party.
Wolfe wrote a book that was part autobiography, and part polemic entitled Scotland Lives: the Quest for Independence. It was published in 1971.