The　core-shelled　structural　electrocatalysts　composed　of　multiple　transition　metal　sulfides　are　of　broad　promise　in　diverse　power　conversion　and　storage　techniques.　Herein,　we　have　employed　a　plausible　strategy　to　synthesize　a　series　of　porous　composite　electrocatalytic　materials　with　hierarchical　architecture　based　on　metal-organic　framework　(MOF)　derivatives　(Bi2S3　@CoS2/MoS2,　CoS2/MoS2,　and　Bi2S3　@MoS2).　Remarkably,　by　virtue　of　the　huge　specific　surface　area,　unique　surface　appearance,　and　the　synergistic　effect　of　multi-metals,　the　catalyst　exhibits　excellent　electrocatalytic　performance　as　a　bifunctional　catalyst　in　dye-sensitized　solar　cells　(DSSCs)　and　hydrogen　evolution　reactions　(HERs).　Herein,　the　quaternary　Bi2S3　@CoS2/MoS2　microspheres　exhibit　remarkable　merits　in　facilitating　the　regeneration　of　iodine　redox　pairs　in　DSSCs　as　well　as　improving　hydrogen　evolution　activity　concerning　CoS2/MoS2　and　Bi2S3　@MoS2　microspheres.　Particularly,　the　DSSCs　with　Bi2S3　@CoS2/MoS2-based　counter　electrode　performed　superior　power　conversion　efficiency　(PCE)　of　9.43　%,　outperforming　that　of　Pt　(7.87　%).　Besides,　a　low　onset　overpotential　of　29.5　mV,　small　Tafel　slope　of　56.2　mV　dec–1,　and　low　overpotential　of　94.7　mV　at　the　current　density　of　10　mA　cm–2　were　delivered　for　Bi2S3　@CoS2/MoS2　as　HERs　electrocatalyst　under　alkaline　environment.　©　2022　Elsevier　B.V.