Highly functionalized sulfone containing scaffolds are ubiquitous and are attracting increasing interest in pharmaceutical and agrochemicals owing to their enhanced activities. Herein, we present an alternative protocol to access highly substituted sulfones from readily accessible olefin feedstocks and sulfinate salts through a DABSO enabled anti-Markovnikov hydrosulfonylation process. Notably, the practical procedure features excellent compatibility with various susceptible functional groups and a broad substrate scope under mild and operationally simple conditions. Gram-scale preparation, post-functionalization of complex molecules, and applications in the synthesis of bioactive compounds underscore the potential in drug discovery.