The power conversion efficiencies (PCEs) of all-polymer solar cells (all-PSCs), usually processed from low-boiling-point and toxic solvents, have reached high values of 18%. However, poor miscibility and uncontrollable crystallinity in polymer blends lead to a notable drop in the PCEs when using green solvents, limiting the practical development of all-PSCs. Herein, a third component (guest) BTO was employed to optimize the miscibility and enhance the crystallinity of PM6/PY2Se-F host film processed from green solvent toluene (TL), which can effectively suppress the excessive aggregation of PY2Se-F and facilitate a nano-scale interpenetrating network morphology for exciton dissociation and charge transport. As a result, TL-processed all-polymer hosted solar cells (all-PHSCs) exhibited an impressive PCE of 17.01%. Moreover, the strong molecular interaction between the host and guest molecules also enhances the thermal stability of the devices. Our host-guest strategy provides a unique approach to developing high-efficiency and stable all-PHSCs processed from green solvents, paving the way for the industrial development of all-PHSCs.