Controlled presentation of biomolecules on synthetic substrates is an important aspect for biomaterials development. If the immobilization of multiple biomolecules is required, highly efficient orthogonal surface chemistries are needed to ensure the precision of the immobilization. In this communication, chemical vapor deposition (CVD) copolymerization is used to fabricate polymer coatings with controlled ratio of alkyne and pentafluorophenyl ester (Pfp‐ester) groups. Cyclic argine‐glycine‐aspartic acid (cRGD) adhesion peptide and epidermal growth factor (EGF) are immobilized through alkyne–azide cycloaddtion (“click” chemistry) and active ester–amine reaction, respectively. Cell studies with human umbilical vein endothelial cells (HUVEC) and A431 cell lines demonstrate the biological activity of the coimmobilized biomolecules. Polymer coatings with bio‐orthogonal functional groups are developed for co‐immobilization of adhesion peptide and growth factor. The coatings are generated by chemical vapor deposition polymerization, with both alkyne and pentafluorophenyl ester which are used to covalently tether the biomolecules. The biological activity of the co‐immobilized biomolecules is demonstrated.