Wolfe joined the SNP in 1959. He stood as the SNP candidate in the 1962 West Lothian by-election against Tam Dalyell, making a stunning impact by coming in second place in an area where the SNP had previously made little impact. The result propelled him into party office as Vice-Chairman for Policy and Publicity in 1964, and then as Senior Vice-Chairman (Deputy Leader) in 1966. Wolfe formed the Social and Economic Inquiry Society of Scotland, a forum committed to advancing the case for independence through statistical research. His idea of fusing the St Andrew's Cross with a thistle led to the creation of a distinctive new SNP logo, which is still in use today. He played a central role in the development of party policy, writing an iconic policy statement, "SNP and You", which radically changed the SNP's outlook, adapting the existing policy on decentralization to accommodate the social strains from ongoing deindustrialization. Wolfe stood as SNP parliamentary candidate for West Lothian at the 1964, 1966, 1970, both elections in 1974, and 1979 general elections.