Since its discovery, controlled/living radical polymerization (CLRP) has proven to be a mature technology for building tailor-made (block) copolymers, functional polymers and polymers with a wide range of biological recognition. Due to these considerable advantages over other synthetic approaches, CLRP techniques have been successfully exploited to construct novel polymer-protein/peptide bioconjugates with a high level of structural control and varied interesting, somehow unexpected, features. A comprehensive review of the recent advances in the rapidly expanding field of bioconjugation is presented and outlines work up to early 2010.