Nanomaterials　with　yolk-shell　structures　are　identified　as　promising　advanced　catalysts　in　energy　conversion　devices　due　to　their　larger　surface　area,　more　efficient　active　sites,　and　shorter　charge　transfer　paths.　In　this　work,　we　developed　a　facile　template　method　to　synthesize　yolk-shell　structured　CoS2/N-doped　C@Co-WS2　(CoS2/NC@Co-WS2)　as　counter　electrode　material　in　dye-sensitized　solar　cells.　In　detail,　zeolitic　imidazolate　framework-67　(ZIF-67)　as　a　template　reacted　with　(NH4)2WS4　through　an　anion　conversion/exchange　processes,　which　was　followed　by　the　subsequent　sulfuration　reaction.　Additionally,　the　influence　of　mass　ratio　between　reactions　on　the　morphologies　and　electrochemical　properties　of　catalysts　were　further　explored.　When　the　mass　ratio　of　the　ZIF-67　precursors　and　(NH4)2WS4　is　5/1,　CoS2/NC@Co-WS2　delivered　a　superior　power　conversion　efficiency　of　9.21%　for　Pt-free　dye-sensitized　solar　cells　which　was　much　higher　than　that　of　Pt　(8.18%).　This　result　could　be　attributed　to　the　coordination　of　multiple　elements,　prominent　yolk-shell　structure,　and　the　largest　surface　area　(110　m2　g−1).　©　2020　Elsevier　Ltd