The results of optical absorption measurements on fine‐grain polycrystalline‐silicon thin films indicate that the singly occupied dangling silicon bond lies 0.65±0.15 eV below the conduction‐band minimum in the grain boundary. The grain boundary band gap is ∼1.0 eV and there is evidence for exponential tailing of the band edges. The optical absorption was determined by photothermal deflection spectroscopy. The dangling silicon bond density has been measured on polycrystalline‐silicon thin films as a function of hydrogen passivation of the grain boundaries and on silicon‐on‐saphhire films. The optical absorption exhibits a defect shoulder which varies as the dangling bond density.