Molybdenum-based　co-catalyst　decoration　is　a　promising　strategy　in　the　construction　of　an　highly　efficient　photocatalyst　composite　for　hydrogen　evolution　utilizing　sunlight.　In　this　work,　a　novel　MoO2-C/CdS　(MOCCS)　ternary　heterojunction　photocatalyst　with　unique　interfacial　microstructures　has　been　successfully　constructed.　The　interfacial　disordered　MoOx　regions,　which　act　as　the　main　active　sites　for　photocatalytic　water　splitting,　can　be　found　in　the　MoO2-C　nanocomposites.　While　for　the　ternary　heterojunction,　the　direct　interfacial　Mo-S　bonds　and　metallic　Cd　can　guarantee　the　high-effect　interfacial　charge　separation　and　transfer　between　MoO2-C　and　CdS　nanorods.　The　as-prepared　MOCCS　composite　shows　a　remarkable　enhancement　of　photocatalytic　H2　evolution　performance　(∼16.08　mmol·h−1　g−1),　which　is　up　to　33　times　as　high　as　that　of　pure　CdS　nanorods.　Photoelectrochemical　analyses　demonstrate　that　the　synergetic　effect　of　unique　interfacial　microstructures　will　result　in　the　efficient　separation　and　reaction　of　the　photocarriers,　and　the　reduced　hydrogen　overpotential　during　photocatalytic　water　splitting　process.　©　2019　Elsevier　B.V.