A novel FeVO₄/g-C₃N₄ composite photocatalyst was synthesized via a simple mixing-calcination method and characterized by various techniques including the Brunauer–Emmett–Teller method, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectroscopy, photoluminescence spectroscopy, and an electrochemical method. The photocatalytic activity was evaluated by degradation of rhodamine B (RhB). Results indicated that the FeVO₄/g-C₃N₄ composite exhibited a much higher photocatalytic activity than pure g-C₃N₄ under visible light illumination. The rate constant of RhB degradation for the optimal FeVO₄/g-C₃N₄ composite (5.0% FeVO₄/g-C₃N₄) is approximately 2.2 times that of pure g-C₃N₄. The formation of a heterojunction structure between FeVO₄ and g-C₃N₄ which efficiently promoted the separation of electron–hole pairs was believed to be the origin of the enhanced photoactivity.