The discharge of wastewater containing hexavalent chromium (Cr(VI)) would cause serious environmental pollution and endanger human health. Design of high-performance and stable photocatalysts for Cr(VI) reduction in neutral solution remain huge challenging. Herein, a novel starfish-like zinc tungstate/zinc benzoate (ZnWO4/Zn(Bro)2) inorganic/organic heterojunction photocatalyst was synthesized via a facile hydrothermal method. The starfish-like zinc tungstate was decorated with uniform dispersed zinc benzoate nanosheets via a self-assembling process, The intimate interface between inorganic and organic phase significantly boosted the transport efficiency of photogenerated carriers and reduced the recombination probability of e- and h+, and enhanced the photocatalytic efficiency for Cr(VI) reduction. the optimized ZWBR-2 composite catalyst displayed conspicuous photocatalytic activity and stability towards the Cr(VI) reduction in neutral solution. This work gives a new perspective to design efficient and promising inorganic/organic heterojunction photocatalyst used in dealing with Cr(VI) in neutral solution.