ABSTRACT AgBr/BiVO4 photocatalysts with heterojunction structures were prepared using a hydrothermal method. To analyse phase composition and microstructure, samples were characterised by X-ray diffraction and scanning electron microscopy, respectively. Photoluminescence measurements were used to characterise the recombination rate of photogenerated electron–hole pairs. The phase structure, chemical state and optical properties of heterojunctions were analysed by UV-visible diffuse-reflectance spectrometry. AgBr/BiVO4 showed high efficiency for the degradation of rhodamine B under visible light irradiation. Hydrothermal temperature and pH values exhibited significant influence on band gap energy and the recombination rate of electron–hole pairs of AgBr/BiVO4, reflective of photocatalytic properties. Results show that at 160°C and pH of 7 AgBr/BiVO4 achieved the best photocatalytic activity, for which the visible light-absorption range of the AgBr/BiVO4 heterojunction was significantly enhanced. Photodegradation catalysis of RhB was most efficiently achieved at a level of approximately 56.72% for a reaction time of 140 min.