Angle-resolved ultraviolet photoelectron spectroscopy (ARUPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy were applied to the investigation of the tilt angles of the naphthalene pendant groups at the surface of a poly(2-vinylnaphthalene) thin film. In contrast to NEXAFS, which provides only an average determination of the tilt angle, ARUPS combined with a sophisticated analysis of photoelectron angular dependence offers more detailed information. It was concluded that the naphthalene pendant groups are tilted randomly at the polymer surface, and that the tilt angle distribution is well described as a three-dimensional isotropic random orientation.