A novel three-dimensional (3D) network rodlike Ag 2 S/ Bi 2 SiO 5 photocatalyst with a p−n heterostructure composed of ultrafine Ag 2 S nanoparticles (NPs) and Bi 2 SiO 5 nanosheets was prepared using an anionic self-regulation strategy by a two-step hydrothermal process. The architecture facilitated the efficient transfer and separation of photogenerated electron−hole pairs. The optimal Ag 2 S/Bi 2 SiO 5 composite (ABSO 0.10 ) exhibited an excellent reduction activity (93.5% Cr(VI) removal in wastewater containing 50 mg•L −1 Cr(VI) within 90 min under visible light), which was about 11.2 and 25.6 times higher than that of the pristine Ag 2 S and virgin Bi 2 SiO 5 , respectively. Assisted by experiments and density functional theory (DFT) calculations, a possible photocatalytic mechanism for Cr(VI) reduction over the Ag 2 S/Bi 2 SiO 5 composite under visible-light irradiation was proposed.