This review summarizes several photochemical methods of immobilization biomolecules on polymer materials in order to enhance its biomedical performance. Proteins such as albumin, polysaccharides such as heparin, other biomolecules such as enzyme, antibody, peptides, DNA fragments and so on are all available by those methods. It can retain the reactivity of immobilized biomolecules and do district designed modification without undermining the substrate performance. Polymer materials immobilized with biomolecules can obtain favorable biocompatibility and biomedical performance.