High-performance non-fullerene OSCs with PCEs of up to ca. 6.0% are demonstrated based on PBDTT-F-TT polymer and a molecular di-PBI acceptor through comprehensive molecular, interfacial, and device engineering. Impressive PCEs can also be retained in devices with relatively thick BHJ layer and processed through non-halogenated solvents, indicating these high-performance non-fullerene OSCs are promising for large-area printing applications.