There is immense promise in photocatalysis for utilizing single-atomic-layer cobalt and tungsten oxide (CoW) on TiO2–BiCu2VO6, ethylene diamine, and reduced graphene-oxide-supported materials. Although there is great excitement surrounding single-metal atom oxide catalysts, converting bulk metal oxides into single-atom oxides remains challenging. In addition, creating high-performance materials for photocatalytic hydrogen (H2) generation and Cr(VI) reduction is crucial and challenging. This work presents a precise catalyst achieved by anchoring a high loading of CoW single metal atom oxide onto the surface of TiO2–BiCu2VO6-rGO through a simple sonication process, even at low temperatures. The prepared TiO2–BiCu2VO6–CoW-ED-rGO (TBCR) catalysts exhibited improved stability when used for hydrogen (H2) generation and Cr(VI) reduction under visible-light illumination. The single Co and W atoms on the TiO2–BiCu2VO6 catalyst demonstrated exceptional performance in H2 generation and Cr(VI) reduction. Through careful experimentation, optimizing the loading of single atoms on the interstitial atomic line of TiO2–BiCu2VO6 significantly enhanced its visible-light absorption capabilities. Using HAADF-STEM, EXAFS, and XANES investigations, cobalt/tungsten single metal atom oxide was determined to be uniformly dispersed over the TiO2–BiCu2VO6 material. The developed photocatalyst showed impressive results with improved H2 generation (36.48 mmol/g/h) and maximum reduction of Cr(VI) (99.4 %). Moreover, by harnessing solar radiation, the photocatalyst can efficiently replace existing noble metal catalysts as a highly effective and durable single-atom catalyst for renewable H2 generation and Cr(VI) reduction.