Luminescence spectra and their variation with temperature have been investigated for solid films of poly(methylphenylsilane) and its branched analogs. Introduction of branching points to the polymers enhances the broad luminescence band in the visible region while suppressing the sharp UV luminescence band due to the resonant recombination of the exciton. The intensity of the visible luminescence is observed to keep on increasing with decreasing temperature in contrast with the nearly temperature‐independent intensity of the resonant luminescence. The behavior is interpreted in terms of phonon‐assisted tunneling between luminescence centers and nonradiative ones. ©1995 American Institute of Physics.