Hollow　structured　nano-materials　based　on　polynary　metallic　sulfides　receive　intensive　investigation　for　new　energy　technologies　such　as　dye-sensitized　solar　cell　and　electrochemical　hydrogen　production　because　of　their　abundant　reserves,　low　cost,　well-defined　void　space,　and　superior　electrochemical　activity.　In　this　work,　WS2-doped　CuCo2S4　(CuCo2S4/WS2)　hollow　nano-prisms　were　successfully　synthesized　and　served　as　extremely　feasible　bifunctional　electrochemical　catalysts　for　solar　cell　and　high-efficiency　hydrogen　production.　In　detail,　copper-cobalt　acetate　hydroxide　nano-prism　precursors　were　used　as　templates　to　react　with　different　mass　of　(NH4)(2)WS4,　and　then　proceeded　to　a　further　calcination　process.　Specifically,　the　surface　morphologies　of　the　hollow　nano-prisms　could　be　effectively　controlled　by　changing　the　mass　ratio　between　the　Cu-Co　nano-prism　precursors　and　(NH4)(2)WS4.　Due　to　the　stable　structures　with　proper　amount　of　WS2　nanoparticles　attaching　to　the　surface,　synergistic　effect,　abundant　active　sites,　and　large　specific　surface　area,　CuCo2S4/WS2-1/1　revealed　an　excellent　power　conversion　efficiency　of　9.50%　comparing　with　Pt　(8.32%)　for　solar　cell　and　displayed　fairly　low　overpotential　of　73.6　mV　at　a　current　density　of　10　mA　cm(-2)　and　quite　small　Tafel　slope　of　54.7　mV　dec(-1)　as　electrocatalyst　for　hydrogen　production　in　0.5　M　H2SO4.