Photoelectric properties of PbTiO3/Si heterostructures were investigated over a broad range of wavelengths. The spectral distribution of the a.c. open-circuit voltage was measured for wavelengths ranging from 0.35 μm to 4 μm. Two local peaks are observed at 0.38 μm and 0.9 μm which can be attributed to band-to-band excitations in PbTiO3 and Si respectively. The shape of the a.c. signal depends both on the light intensity and on the wavelength. When the heterojunction is reverse-biased, a d.c. photocurrent was observed which has a similar spectral distribution as the a.c. open-circuit voltage.