In　this　work,　a　new　kind　of　CdS/CdSe/CuS　hollow　nanospheres　(HNPs)　is　successfully　synthesized　by　one-step　synthesis　via　vulcanization　and　selenization　in　aqueous　solution,　without　using　any　additional　templates,　for　the　first　time.　The　three　components　of　CdS,　CdSe　and　CuS　in　the　HNPs　are　thoroughly　combinated　with　each　other　at　nano-scale,　which　creates　a　large　quantity　of　intimate　contact　interfaces.　As　a　result,　the　optimal　CdSe30Cu2S　HNPs　exhibit　an　excellent　photocatalytic　H2　evolution　rate　of　723　μmol　h-1　(10　mg　of　catalyst)　without　adding　any　noble　metal　co-catalysts,　which　is　6.5　times　higher　than　that　of　the　pristine　CdS　HNPs.　The　hollow　structure　enhances　the　light　absorption　and　provides　the　inner　surface　as　active　sites　for　the　infiltrated　water　to　receive　the　inner-shell　electrons　quickly　for　H2　evolution　and　the　CdS/CdSe/CuS　heterostructure　with　CuS　acting　as　the　co-catalyst　forms　three　charge　transfer　pathways　to　promote　the　separation　and　migration　of　the　photo-induced　electrons　and　holes,　resulting　in　the　enhanced　photocatalytic　performance.　This　work　may　provide　a　strategy　for　the　design　and　synthesis　of　other　photocatalysts　for　highly　efficient　H2　evolution.　This　journal　is　©　The　Royal　Society　of　Chemistry.