The development of polymerized small molecule acceptors (PSMA) has pushed all-polymer solar cells (all-PSCs) to break through power conversion efficiency (PCE) of 16–17%. However, these PCEs are obtained by halogenated solvents processing, which will cause serious harm to the environment and human health. To make the PSMA-based all-PSCs suitable for non-halogenated solvent processing, we introduced PZT into a typical high-efficiency all-PSCs system based on PBDB-T:PYF-T, to improve the solubility of PYF-T in non-halogenated solvent toluene (TL...