The La2/3Cal/3Mn03_σ film has been deposited on the （001） SrTiO3 substrate and its temper- ature-dependent photoconductive properties have been investigated from 80 to 300 K. The La2/3Cal/3MnO3-σ film has a novel photoelectric property due to its oxygen-deficient structure. We observed laser-induced giant negative photoresistance of the sample in a wide temperature range. The change rate of negative photoresistance was nearly 100% at the low temperature when the sample was irradiated by 532 nm laser. In addition, this effect was sensitive to the power of laser irradiation. The oxygen-deficiency of La2/3Cal/3Mn03-σ film seems to have an impact on the laser-induced resistance variation. The experimental results made the La2/3Cal/3MnO3_σ film a promising application as a photoswitch device.