Growth and electronic structure of pentacene film on silicon oxide before and after octadecyltrichlorosilane (OTS) treatment have been studied by photoelectron spectroscopy and photoelectron emission microscopy. On the OTS-treated surface, due to the weak interaction between the substrate and pentacene, the diffusion of pentacene is enhanced and domain size gradually grows, leading to a gradual change of the HOMO offset position. On the bare silicon oxide, the change of the HOMO position is marginal because of relatively strong interaction between the substrate and pentacene from the beginning.