Solar light driven hydrogen production from water splitting and oxidation of biomass-derivatives is attractive for the conversion of solar energy to high value-added chemicals. The fabrication of heterostructure photocatalysts with matched band structure between two semiconductors is a promising approach for efficient photocatalysis. In this work, a novel In2O3/In2S3 heterostructured hollow fiber photocatalyst was successfully fabricated through two-step ion exchange and chemical bath deposition methods, where the In2S3 nanoparticles (NPs) anchored on the surface of In2O3 hollow fibers via strong interfacial interaction between the In2O3 (222) and In2S3 (220) facets. The photocatalyst was used for efficient visible-light-driven photocatalytic hydrogen production integrated with selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF). Compared with pristine In2O3 and In2S3, the optimal In2O3/In2S3 heterostructure exhibits an enhanced photocatalytic hydrogen production rate (111.2 μmol h−1 g−1), HMF conversion efficiency (56%) and DFF selectivity (68%) under visible light irradiation. The experimental and theoretical investigations illustrate the phase interface between well matched In2O3 (222) and In2S3 (220) facets gives rise to facilitated photogenerated charge separation and transfer. This study presents the development of high-performance heterostructured photocatalysts for high efficient hydrogen production coupled with biomass oxidation.