The synthesis of novel alternating polyketones bearing pendent bioactive moieties is presented. These materials were prepared by palladium catalyzed coordination polymerization of carbon monoxide and alpha-olefins substituted with protected tyrosine or with dipeptide sequences such as tyrosine-glycine, tyrosine-alanine, and tyrosine-valine. Copolymerization experiments of CO with monomers containing vitamin E or testosterone were also successfully performed under mild reaction conditions. The dicationic Pd (II) bis(phoshine) complex [Pd(dppp)(NCCH3)(2)](BF4)(2) was used as catalyst precursor giving rise to macromolecules with well-defined structures.