In this work, we have employed chemical bath deposition (CBD) method to obtain nanocrystalline PbS thin films in the presence of polyethylene oxide (PEO). The spectral response of Au/PbS-pSi(100)/Al Schottky photodiodes at different PEO amount were studied. The response exhibits a combined effect of photogeneration in the heterojunction (HJ) Si side and PbS. Spectral response were observed progressively at shorter wavelength due to the surface absorption. The peak centered at 410 nm properly corresponds to photo-exited holes being injected from PbS to the Si substrate. The intensity of the peak of R(λ) increases with PEO amount, this increasing was attributed to the decreasing of band gap (Eg).