The　hierarchical　polymetallic　sulfide　electrocatalysts　are　endowed　with　high　expectations　in　various　energy　conversion/storage　fields.　Herein,　a　facile　two-step　solvothermal　method　was　employed　to　synthesize　a　series　of　hierarchical　transition　metal　sulfide　nanospheres　with　defined-well　yolk-shelled　structures　(Co9S8-Ni3S2@WS2,　Co9S8@WS2　and　Ni3S2@WS2).　Noteworthily,　the　resultant　samples　as　the　bifunctional　electrocatalysts　for　the　dye-sensitized　solar　cells　possessed　prominent　electrocatalytic　performances.　Benefiting　from　the　higher　specific　surface　area,　unique　morphology,　the　synergistic　effect　of　multi-elements　and　more　favorable　chemical　compositions,　the　quaternary　Co9S8-Ni3S2@WS2　nanospheres　showed　great　advantaged　features　at　promoting　the　reduction　of　triiodides　in　comparison　with　ternary　Co9S8@WS2　and　Ni3S2@WS2　nanospheres.　Among　these　samples,　the　counter　electrode　with　Co9S8-Ni3S2@WS2　catalysts　exhibited　a　noteworthy　power　conversion　efficiency　of　9.67%　for　solar　cell,　which　was　much　superior　to　that　of　Pt　(8.16%).