In this work, a nonfullerene polymer solar cell (PSC) based on a wide bandgap polymer donor PM6 containing fluorinated thienyl benzodithiophene (BDT-2F) unit and a narrow bandgap small molecule acceptor 2,2'-((2Z,2'Z)-((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile (IDIC) is developed. In addition to matched energy levels and complementary absorption spectrum with IDIC, PM6 possesses high crystallinity and strong π-π stacking alignment, which are favorable to charge carrier transport and hence suppress recombination in devices. As a result, the PM6:IDIC-based PSCs without extra treatments show an outstanding power conversion efficiency (PCE) of 11.9%, which is the record value for the as-cast PSC devices reported in the literature to date. Moreover, the device performances are insensitive to the active layer thickness (≈95-255 nm) and device area (0.20-0.81 cm2 ) with PCEs of over 11%. Besides, the PM6:IDIC-based flexible PSCs with a large device area of 1.25 cm2 exhibit a high PCE of 6.54%. These results indicate that the PM6:IDIC blend is a promising candidate for future roll-to-roll mass manufacturing and practical application of highly efficient PSCs.

High‐Performance As‐Cast Nonfullerene Polymer Solar Cells with Thicker Active Layer and Large Area Exceeding 11% Power Conversion Efficiency