Polyketides are secondary metabolites biosynthesized by the iterative Claisen condensation of malonate units. Despite utilizing only a small set of biochemical transformations, the polyketide biosynthetic machinery yields products of striking structural complexity and diversity. Recently, a new polyketide alkylation pathway was characterized that allows access to "beta-branched" structures. This Highlight will describe this alkylation sequence, with special emphasis on its parallels to isoprenoid biosynthesis from primary metabolism and the scope of structures accessible via this pathway.