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The hole transporting layers (HTLs) between the electrode and light absorber play a vital role in charge extraction and transport processes in organic solar cells (OSCs). Herein, a bilayer structure HTL of CuSCN/TFB is formed by soluble copper(I) thiocyanate (CuSCN) and poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(4,4'-(N-(4-butylphenyl)))] (TF. The excellent charge extraction capability is proved in nonfullerene PM6Y6 and fullerene PTB7-ThPC71BM blend system-based cells. The introduction of TFB tunes the work function and polishes the