Recently, main-chain twisted small molecules are attractive as electron-acceptors in polymer solar cells (PSCs) for their upshifted molecular energy levels, enhanced extinction coefficients, and better charge extraction properties along with longer carrier lifetimes and lower recombination rates relative to their planar analogues, which are conducive to the power conversion efficiency (PCE) promotion of PSCs. To further probe the "structure-performance" correlation of main-chain twisted acceptors, in particular the monofluorine-substituted sites on the performances of the resultant acceptors, two new main-chain twisted small molecules were synthesized, in which a fluorine atom was introduced at different sites on the end-capping group 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN). Although fine structural modification was adopted, quite different performances were obtained for the two acceptors. Compared to the 3-fluorinated analogue (i-IEICO-F3), a mixture of 4-fluorinated and 5-fluorinated isomers (i-IEICO-2F) exhibited a higher dipole moment, enlarged molar extinction coefficient with a bathochromic-shifted absorption region, suppressed charge recombinations with balanced charge mobilities, and slightly enhanced crystallinity. In combination with a fluorobenzotriazole-based medium-band gap polymer (J52), a high efficiency of 12.86% was resultantly achieved in an i-IEICO-2F-based device, which is superior to the result (7.65%) of the i-IEICO-F3 device, revealing the importance of monofluorinated positions on the performances of main-chain twisted non-fullerene acceptors.