CuO nanowires (NWs) with the diameters ranging from 130 to 275 nm have been successfully prepared by electrospinning technique, followed by a calcination process. Inverted planar heterojunction perovskite solar cells (PSCs) with the structure of indium tin oxide/CuO NWs/poly(3,4-ethylenedioxythiophene) (PEDOT):poly(styrenesulphonate) (PSS)/CH3NH3PbI3/phenyl C-61-butyric acid methyl ester/Bphen/Ag were designed, achieving a best power conversion efficiency (PCE) of 16.87%, which is 21% improvement compared to that of the control PSCs without CuO NWs. By the characterizations of an optical microscope, X-ray diffraction, and scanning electron microscopy, it was found that CuO NWs have uniform morphology and orderly arrangement. Electrochemical impedance spectrometry and external quantum efficiency were used to reveal the effect of CuO NWs on the performance of PSCs. Compared to ZnO NWs with the same diameters and quantitative analysis based on a simple model, we conclude that the improvement of PCE by about 13% can be ascribed to the increase of the PEDOT:PSS/CH3NH3PbI3 interface area and the remaining increase of 8% can be attributed to the higher hole mobility of the CuO NWs/PEDOT:PSS composite film. The results PSCs will have a significant enhancement when the optimal CuO NWs are introduced into the charge transport layer.