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All‐polymer solar cells (all‐PSCs) exhibit excellent stability and readily tunable ink viscosity, and are therefore especially suitable for printing preparation of large‐scale devices. At present, the efficiency of state‐of‐the‐art all‐PSCs fabricated by the spin‐coating method has exceeded 11%, laying the foundation for the preparation and practical utilization of printed devices. A high power conversion efficiency (PCE) of 11.76% is achieved based on PTzBI‐Si:N2200 all‐PSCs processing with 2‐methyltetrahydrofuran (MTHF, an environmentally friendly solvent) and preparation of active layers by slot die printing, which is the top efficient for all‐PSCs. Conversely, the PCE of devices processed by high‐boiling point chlorobenzene is less than 2%. Through the study of film formation kinetics, volatile solvents can freeze the morphology in a short time, and a more rigid conformation with strong intermolecular interaction …