We report a facile way to produce printable highly conductive cathode interfacial layer (CIL) for efficient polymer solar cells (PSCs) by sensitizing ZnO nanocrystals (NCs) with a blue fluorescent conjugated polymer, poly(9, 9-bis-(6'-diethoxylphosphorylhexyl) fluorene) (PFEP). Herein, PFEP plays dual distinctive roles in the composite. Firstly, PFEP chains can effectively block the aggregation of ZnO NCs, leading to uniform and smooth film during solution processing via assembly on ZnO NC surfaces through their pending phosphonate groups. Secondly, PFEP can greatly improve the conductivity of ZnO NCs by charge transfer doping, that is the charge transfer from the sensitizer driven by electron-chemical potential equilibrium, which could be even more pronounced under light illumination because of light excitation of PFEP sensitizer. The increased conductivity in ZnO-PFEP layer renders more efficient electron transport and extraction compared to pristine ZnO layer. This ZnO-PFEP CIL was successfully applied to PSCs based on three polymer donor systems with different band-gaps, and efficiency enhancements from 44 to 70% were observed compared to those PSCs with pristine ZnO CIL. The highest efficiency of 7.56% was achieved in P(IID-DTC):PC70BM-based PSCs by using ZnO-PFEP film as CIL. Moreover, the enhanced conductivity due to the charge-transfer doping effect allows thick ZnO-PFEP film to be used as CIL in high-performance PSCs. Both the high conductivity and good film-forming properties of ZnO-PFEP CIL are favorable for large-scale printable PSCs, which is also verified by high-efficiency PSCs with ZnO-PFEP CIL fabricated using doctor-blading, a large-scale processing technique. The work provides an efficient printable cathode interfacial material for efficient PSCs.