To achieve high-performance dye-sensitized solar cells (DSSCs), it is essential to establish new and effective photoelectrode materials. Herein, we report the successful synthesis of heterojunctions including Cu-based delafossite oxide CuCoO2and ZnO derived from zeolitic imidazolate framework-8 (ZIF-8). The layered polyhedral nanocrystals of CuCoO2produced through a feasible low temperature hydrothermal process and the faceted nanocrystals of ZnO were achieved by heat treatment of ZIF-8. The composite heterostructures were applied as photoelectrodes in DSSCs assembled using dye N719 and a Pt counter electrode. The physicochemical characteristics (XRD, FESEM, EDAX, mapping, BET, DRS), dye loading, and photovoltaic properties (J–V, EIS, IPCE) of the fabricated materials were studied and fully discussed. Results revealed that addition of CuCoO2to ZnO significantly improved theVoc,Jsc, PCE, FF, and IPCE. Among all cells, CuCoO2/ZnO (0.1 : 1) showed the best performance (PCE = 6.27%,Jsc= 14.56 mA cm−2,Voc= 687.84 mV, FF = 62.67%, IPCE = 45.22%) and acted as a promising photoanode in DSSCs.