p-type CuCoO2/n-type SnO2 heterostructured photocatalysts were produced and used, for the first time, in photocatalysis applications for the removal of organic pollutants in wastewater. The heterostructures were obtained by decoration of hydrothermally derived CuCoO2 nanoparticles (NPs) on electrospun SnO2 nanofibers (NFs). Microstructural, morphological, optical, and electrochemical properties of SnO2, CuCoO2, and the heterostructures were characterized in detail. The photocatalytic activities of CuCoO2/SnO2 (0.25–1.25 wt% CuCoO2) were systematically examined and the highest activity was obtained for the SnO2 sample containing 0.35 wt% CuCoO2 and almost all the methylene blue (MB) dye (98.1 %) was degraded within 90 min. Compared to the SnO2, 0.35 wt% CuCoO2-SnO2 exhibited 83 % increase in degradation rate of MB dye. This increase in photocatalytic activity was attributed to the narrow band gap CuCoO2 absorbing more light together with SnO2, thus generating more electron (e-)-hole (h+) pairs and more successful charge separation thanks to the p-n junction they formed.