Bi/Bi2MoO6 composite was prepared via a facile one-step hydrothermal reduction method and its photoelectric property was investigated. During the solvent-controlled reaction process, lysine performed as the reductant to in situ reduce Bi3+ to metallic Bi. XRD, SEM, TEM, HRTEM, XPS and FT-IR were used to characterize the morphology, structure and chemical composition of the samples obtained. Bi/Bi2MoO6 composites have special structure of Bi2MoO6 nanosheets surrounding on the surface of Bi microspheres, besides, the Bi2MoO6 nanosheets have a thickness of 10–20nm. Furthermore, electrochemical test results show that the Bi/Bi2MoO6 composites can significantly enhance the separation efficiency of photogenerated charge carriers, the photocurrent of Bi/Bi2MoO6 composites prepared with 4mmol lysine is about 15 times to pure Bi2MoO6.