We design and synthesize four fused-ring electron acceptors based on 6,6,12,12-tetrakis­(4-hexylphenyl)-indacenobis­(dithieno­3,2-b;2′,3′-d­thiophene) as the electron-rich unit and 1,1-dicyanomethylene-3-indanones with 0–2 fluorine substituents as the electron-deficient units. These four molecules exhibit broad (550–850 nm) and strong absorption with high extinction coefficients of (2.1–2.5) × 105 M–1 cm–1. Fluorine substitution downshifts the LUMO energy level, red-shifts the absorption spectrum, and enhances electron mobility. The polymer solar cells based on the fluorinated electron acceptors exhibit power conversion efficiencies as high as 11.5%, much higher than that of their nonfluorinated counterpart (7.7%). We investigate the effects of the fluorine atom number and position on electronic properties, charge transport, film morphology, and photovoltaic properties.