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.　(C)　2022　Elsevier　B.V.　All　rights　reserved.