A series of Ag2S/Ag2WO4 composite microrods with different Ag2S contents (10–50 wt%) were synthesized via a facile successive precipitation route. The texture and optical properties of the pure Ag2S, Ag2WO4, and Ag2S/Ag2WO4 composites were intensively characterized by some physicochemical characterizations like N2 physical adsorption, x-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, Ultraviolet–visible spectroscopy, x‐ray photoelectron spectroscopy, photoluminescence spectroscopy, and photocurrent measurements. Under visible light irradiation, different organic dyes, e.g., methylene blue and methyl orange dye were applied to evaluate the photocatalytic performances by their photocatalytic degradation reactions. The Ag2S/Ag2WO4 composite microrods exhibited superior photocatalytic activity and stability. The high crystallinity of Ag2WO4 and improved texture properties of Ag2S/Ag2WO4 resulted in their enhanced photocatalytic property. More importantly, the Ag2S/Ag2WO4 heterojunctions with matching electronic band structures obviously enhanced the separation of photo‐generated electrons and holes, further promoting the photocatalytic reaction.