Optical properties and the photovoltaic effect in Pb2CrO5thin films, which are prepared by an electron‐beam evaporation technique, are investigated. From the main peaks of the x‐ray diffraction (XRD) patterns, which depend on the preparation condition, thin films are classified into three types: (1) (020), (2) (310), and (3) (200). The sample with a (310) main reflection has a similar XRD profile to that of the bulk material. A device to measure the photovoltiac response in the thin films has one pair of semitransparent Au electrodes on the same surface. All the Pb2CrO5thin films had a photovoltaic response. The (310) sample shows the largest photosensitivity. In this sample the saturation photovoltage is 1.16 V at a light intensity of 23.25 mW/cm2. The absorption constant (&agr;) of thin films in the visible region ranges between 4×103and 1×105cm−1. A band‐gap energy of 2.3–2.4 eV is obtained from both plots of &agr;2and photovoltage as a function of photon energy.