Photocatalytic hydrogen evolution is a promising approach for direct solar-to-fuel conversion. Although significant research efforts have been put on the development of lead-free metal halide perovskites to reach excellent optoelectronic properties, their rational design for efficient heterojunction photocatalytic systems still poses challenges. Here, we report a new strategy to tailor the interface of hybrid tri(dimethylammonium) hexaiodobismuthate (DMA3BiI6) and amorphous molybdenum sulfide (a-MoSx) heterojunctions. Specifically, a-MoSx was prepared with abundant apical S2– or bridging S22– ligands to allow coupling with DMA3BiI6 via an interfacial Mo–S–Bi linkage. The as-obtained heterostructures were found to show an improved visible-light-driven photocatalytic hydrogen evolution in hydroiodic acid splitting under mild conditions reaching a superior hydrogen evolution rate of around 750 µmol g−1 h−1 and an apparent quantum efficiency (AQE) of 13.0 % at 420 nm. The high activity was kept after a long-term performance test for 3 days.