The functionalization of polymer surfaces via surface-initiated atom transfer radical polymerization (ATRP) is of crucial importance to prepare various functional materials. It is generally complicated to conduct ATRP on different organic material surfaces. In this work, a facile photoinduced one-step method was first developed for the covalent immobilization of ATRP initiators on the C-H group-containing substrates such as biaxially oriented polypropylene (BOPP). The C-H bonds of precise location of inert polymer surfaces were readily transferred to bromoalkyl initiator, followed by ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and glycidyl methacrylate (GMA), respectively, to produce the resultant patterned BOPP-g-P(DMAEMA) and BOPP-g-P(GMA) films. The epoxy groups of the P(GMA) microdomains can be aminated for covalently coupling IgG, while the P(DMAEMA) microdomains were used for immobilizing IgG via electronic interactions. The resultant IgG-coupled microdomains could interact with the corresponding target proteins, anti-IgG.