Alkylation reactions utilizing nontoxic Lewis acid catalysts and "green" alkylating reagents are of high interest due to the continuous need for environmentally benign C-C and C-X bond formation. This article shows recent advances in Bi(III)-catalyzed alkylations of arenes, 2,4-pentanediones and various oxygen-and nitrogen-containing nucleophiles. Instead of toxic alkyl halides, the electrophilic components for these transformations were benzyl and propargyl alcohols as well as substrates with activated double bonds such as styrenes. The fact that Bi(III) salts are capable of activating both σ-and π-donors highlights their unique character as versatile catalysts for catalytic alkylation reactions. In addition, Bi(III) salts are less toxic and cheaper than other Lewis acids that have been described for similar transformations.