Excitation energy transfer in polysilane-silica hybrid thin films prepared by a sol-gel method have been studied in terms of steady-state and time-resolved photoluminescence (PL) at 10 K. It is found that with decreasing polysilane concentration in the hybrid thin films, the degree of the PL linear polarization memory is increased and the mean PL lifetime is gradually increased. These results can be interpreted in terms of the spatial confinement of excitation energy within polysilane chains in the hybrid thin films because of the increase in the interchain separation. The information obtained here provides insights for optimizing nanostructured materials for use in optoelectronic devices.