Development of heterostructures is one of the constructive strategies for enhancing the photocatalytic activity. Here, novel CuFeO 2 -ZnO heterostructures with different weight percentage (CuFeO 2 = 0.5, 1, 5, 10%) were prepared by two-step precipitation-hydrothermal process. The structural confirmation was done by XRD and Raman analysis. The photocatalytic efficiency of the heterostructures was assessed by the degradation of methylene blue under sunlight. CuFeO 2 -ZnO heterostructures enhanced the photocatalytic performance compared to pure ZnO and CuFeO 2 . Among all, 5 wt % of CuFeO 2 on ZnO exhibited 100% degradation with 16 fold faster kinetics than ZnO. Time-resolved photoluminescent analysis revealed the increase in lifetime of charge carriers in the heterostructure. The band alignments of ZnO and CuFeO 2 , evaluated by Mott–Schottky revealed the existence of Type 1 heterostructures. Further, the heterostructures exhibited good recyclability. Thus, the present work demonstrates the use of p-type CuFeO 2 and n-type ZnO heterostructures as potential photocatalysts.