In this study, a novel nanocomposite, carbon/SnS with 3D hierarchical macroporous (MCS), was successfully prepared for rapid photocatalytic treatment of hexavalent chromium (Cr(VI)). The 3D macroporous carbon (MC) can be obtained through a simple carbonization process of loofah. Since the MCS has a large specific surface area, it can provide numerous photocatalytic active sites and has excellent adsorption properties for the Cr(VI). In addition, the excellent electrical conductivity and unique hierarchical nanoarchitecture of macroporous biomass carbon could rapidly absorb the Cr(VI) from wastewater and provide electron transport tunnel for rapid charge separation/transport to suppress hole electron recombination. It is confirmed that such three dimensional photocatalytic material can quickly purify Cr(VI)-containing wastewater under mild visible light irradiation, with a efficiency of 63.2% Cr(VI) reduction within 120 mins. Besides the high visible light-driven photocatalytic activity, MCS also exhibits excellent cycling stability. In addition, the SEM images of MCS before and after photocatalytic removal of Cr(VI) indicate that the morphology of composite was perfectly maintained and no peeling-off of SnS was observed. More importantly, this study demonstrated that MCS can be used for practical applications due to its stability and economic availability.