Two ternary materials systems, which comprise two-photon initiators, oligomer and poly(methyl methacrylate), were prepared. A polymeric waveguide film was manufactured by spinning the materials on ITO, and the two-photon initiated photopolymerization(TPIP) was carried out successfully in the waveguide film. Consequently, an approach using TPIP is demonstrated for fabrication of grating in a thin polymeric film possessing waveguide properties. The results show that the resulted grating can manipulate and couple light.