Highly efficient polymer solar cells (PSCs) are demonstrated by introducing environmentally friendly CuOx as hole extraction anode buffer layer. The CuOx buffer layer is prepared simply via spin-coating 1,2-dichlorobenzene solution of Copper acetylacetonate on the ITO substrate and thermal transformation (at 80 °C) in air. Remarkable improvements in the open-circuit voltage (Voc) and short-circuit current density (Jsc) of the PSCs could be achieved upon the introduction of CuOx buffer layer. The study about the effect of CuOx interfacial layer on the device resistances demonstrates that insertion of CuOx layer can decrease the whole resistance of the PSCs. For the devices based on P3HT:PCBM, the power conversion efficiency (PCE) was increased from 2.8% (the reference device without buffer layer) to 4.1% via introduction of CuOx hole extraction layer. The PCE of the PSC was further increased to 6.72% when ICBA used as an alternative acceptor to PCBM. The much higher PCE of 7.14% can be achieved by adopting PBDTTT-C, a low band gap conjugated polymer, as donor material. The results demonstrate that CuOx has great potential as a hole extraction material for highly efficient PSCs.