A novel BiNbO4/Bi2S3 nanocomposite was successfully synthesized by combining precipitation, heat‐treatment, and ion exchange technique. The corresponding crystal structure, morphology, chemical components, and adsorption isotherm were fully characterized. The visible‐light photocatalytic performance was investigated in the degradation reaction of Rhodamine B (RhB). Compared to the conversions obtained using BiNbO4 (47%) or Bi2S3 (52%) as the photocatalyst (80 min), BiNbO4/Bi2S3 composite demonstrated a much higher photocatalytic efficiency with conversion up to 87% and great durability. The best fitting of photodecomposition of RhB into a first‐order reaction gave an observed rate constant of kobs= 3.46 ± 0.33 × 10−2 min−1 (t1/2=20.0 min). Our active species trapping experiment confirms that photoexcited holes and •O2− radicals formed in situ under photoexcitation directly oxidize the dye molecules. The improved photocatalytic activity was likely due to the decrease of charge recombination rate resulted from possible interfacial charge transfers through the heterojunction.