We have found a new photoluminescence (PL) band with a maximum at 0.9 eV and a halfwidth of 0.1 eV at 4.2 K in polycrystalline Si thin films deposited on glass at 625 °C. The PL band strongly shifts toward low energy with increasing the temperature (1.3 meV/K) and toward high energy with increasing the excitation intensity. Hydrogenation of polycrystalline Si enhances the PL intensity by factor of 3 to 5. The luminescence characteristics are consistent with radiative recombination of electrons and holes trapped in tail states of the conduction and the valence band, respectively. Excellent agreement is achieved between the 0.9 eV band shape and theoretical calculations based on a band‐tail recombination. It is also argued that a corresponding luminescence spectroscopy provides a new possibility for band‐tail diagnostics in polycrystalline Si thin films. ©1995 American Institute of Physics.