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[Display omitted] • Photo-redox dual reaction for H 2 -evolution integrated with biomass conversion. • A novel bifunctional honeycomb hierarchical structured 3D/3D ReS 2 /ZnIn 2 S 4 -S v. • Nanoengineering and electronic modulation of ZnIn 2 S 4 are employed. • Superior H 2 and furfural yields of 1.08 and 0.71 mmol·g−1·h−1, respectively. • Efficient strategy to convert biomass materials into high value-added products. Photo-redox dual reaction system is an emerging strategy for H 2 -evolution integrated with biomass conversion, which exhibits promise to overcome sluggish water oxidation during overall water splitting. Constructing efficient catalytic materials with strong sunlight response and rapid optoelectronic dynamics remains a significant challenge. Herein, we design and fabricate a novel bifunctional honeycomb hierarchical structured 3D/3D ReS 2 /ZnIn 2 S 4 -S v heterojunction for efficient photocatalytic H 2 -evolution coupled with high value-added biomass conversion, in which S v can be created in situ under NH 2 OH·HCl-assisted hydrothermal condition. The nanoengineering and electronic modulation of ZnIn 2 S 4 by ReS 2 and S v enable its large specific surface area, rapid charge separation, and suppressed carrier recombination, which is beneficial for photocatalytic reactions. As a result, the optimized 20 % ReS 2 /ZnIn 2 S 4 -S v exhibits superior H 2 and furfural generation rates of 1.08 and 0.71 mmol·g−1·h−1, respectively. This work highlights an efficient photocatalyst and a new strategy for this bifunctional photocatalytic system of H 2 -evolution integrated with biomass conversion. [ABSTRACT FROM AUTHOR]