Herein, porous Bi/Bi₂MoO₆ nanoparticles have been prepared by a facile in-situ reduction approach. Moreover, the morphology and Bi content of product could be controlled by varying the reaction time. By controlled fabrication, the desired porous Bi₂MoO₆ nanostructure with incorporation of Bi was obtained and exhibited high photoelectric and photocatalytic activity. In particular, the samples yield a photocurrent density of 320 μA cm⁻², which is 3.2 times that of the pure Bi₂MoO₆ nanosheet (100 μA cm⁻²) under the same conditions. UV/Vis diffuse reflectance spectroscopy analysis confirmed the surface plasmon resonance in the as-prepared porous nanoparticles. The improved photoelectric properties could be the synergistic effect of the porous structure with large surface area and effective electron-hole separations between Bi and Bi₂MoO₆.