High-valence　cobalt　sites　are　considered　as　highly　active　centers　for　the　oxygen　evolution　reaction　(OER)　and　their　corresponding　construction　is　thus　of　primary　importance　in　the　pursuit　of　outstanding　performance.　Herein,　we　report　the　design　and　facile　synthesis　of　abundant　high-valence　cobalt　sites　by　introducing　Zn2+　into　CoFe　Prussian　blue　analogues　(PBAs).　The　modification　results　in　the　drastic　morphological　transformation　from　a　pure　phase　(CoFe-PBA)　to　a　three-phase　composite　(CoFeZn-PBA),　with　a　significant　increase　not　only　the　amount　of　highly　oxidized　Co　sites　but　the　specific　surface　area　(by　up　to　4　times).　Moreover,　the　obtained　sample　also　exhibits　outstanding　electric　conductivity.　Consequently,　an　excellent　OER　performance　with　an　overpotential　of　343　mV@10　mA　cm(-2)　and　a　Tafel　slope　of　75　mV　dec(-1)　was　achieved　in　CoFeZn-PBA,　which　outperforms　the　commercial　IrO2　catalyst.　Further　analysis　reveals　that　CoFeZn-PBA　becomes　(oxyhydr)oxides　after　the　OER.