In this paper, a polymeric coating based on the modified chlorinated polypropylene (CPP) emulsion was synthesized, methyl methacrylate (MMA), butyl acrylate (BA) and acrylic acid (AA) were grafted onto CPP backbone and phase inversion was conducted to obtain waterborne emulsion. Results showed that the concentration of initiator (BPO) had the greatest effect on graft copolymerization. The concentration of emulsifier and temperature influenced the results of phase inversion. Besides, the thermal performances of modified CPP were better than untreated one. In addition, the coating obtained in optimum condition had excellent adhesion to BOPP film, and apparently improved the printing quality of the film. The printability promotion should be attributed to the different movement trend of coating's polar and un-polar chains during the baking step, as well as the subsequent formations of new coating/substrate and coating/ink interface layer.