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New breakthroughs are expecting to be achieved based on the discovery of novel interfacial materials for polymer solar cells (PSCs). Herein, the simple and facial approach of spin-coating technology with post heat and ultraviolet-ozone treatment is performed on niobium oxalate to prepare Nb 2 O 5 interfacial layer with ultra-high transmittance. The ultraviolet photoemission spectroscopy results confirm that Nb 2 O 5 with a work function of 4.85 eV is suitable for employing as anode buffer layer (ABL). The average power conversion efficiencies (PCEs) of the P3HT:PCBM-based fullerene devices with Nb 2 O 5 ABL reaches to 4.01%, surpassing that (3.69%) of the control devices with ITO/PEDOT:PSS ABL. Further investigations on the PBDB-T:ITIC-based non-fullerene PSCs with Nb 2 O 5 ABL demonstrate that a PCE as high as 8.67% can be reached, which is superior to that of device modified by PEDOT:PSS ABL (8.03%). Namely, 8% efficiency improvement in PSCs based on fullerene and non-fullerene acceptors realized as compared to the control devices with PEDOT:PSS ABL. [ABSTRACT FROM AUTHOR]