Since poly(dimethylsiloxane)-modified poly(amic acid) was not wetted by the photoresist, poly(dimethylsiloxane-co-diphenylsiloxane)-modified poly(amic acid) was synthesized to improve the wettability of photoresist. From a study on dynamic contact angles of water, the initial advancing contact angles on poly(dimethylsiloxane)-modified poly(amic acid) and those on poly(dimethylsiloxane-co-diphenylsiloxane)-modified poly(amic acid) are almost the same, but the equilibrium advancing contact angles on poly(dimethylsiloxane-co-diphenylsiloxane)-modified poly(amic acid) are much smaller than those on poly(dimethylsiloxane)-modified poly(amic acid). The decrease in equilibrium advancing contact angles on poly(dimethylsiloxane-co-diphenyisiloxane) appears to indicate migration of phenyl groups to the surface in the polar environment. Thus, photoresist could be wetted on the poly(dimethylsiloxane-co-diphenylsiloxane)-modified poly(antic acid) film. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS) were used to investigate the orientation and surface migration of molecules in poly(dimethylsiloxane-co-diphenylsiloxane).