Indacenodithienothiophene (IDTT)-based postfullerene electron acceptors, such as ITIC (2,2'-[[6,6,12,12-tetrakis (4-hexylphenyl)-6,12-dihydrodithie no [2,3-d:2',3'-d']-s-indaceno [1,2-b:5,6-b']dithiophene-2,8-diyl]-bis-[methylidyne(3-oxo-1H-indene-2,1 (3H)-diylidene) This[propanedinitrile]), have become synonymous with high power conversion efficiencies (PCEs) in bulk heterojunction (BHJ) polymer solar cells (PSCs). Here we systematically investigate the influence of end-group fluorination density and positioning on the physicochemical properties, single-crystal packing, end-group redistribution propensity, and BHJ photovoltaic performance of a series of ITIC variants, ITIC-nF (n = 0, 2, 3, 4, and 6). Increasing n from 0 -> 6 contracts the optical bandgap, but only marginally lowers the LUMO for n > 4. This yields enhanced photovoltaic short-circuit current density and good open-circuit voltage, so that ITIC-6F achieves the highest PCE of the series, approaching 12% in blends with the PBDB-TF donor polymer. Single-crystal diffraction reveals that the ITIC-nF molecules cofacially interleave with ITIC-6F having the shortest pi-pi distance of 3.28 angstrom. This feature together with ZINDO-level computed intermolecular electronic coupling integrals as high as 57 meV, and B3LYP/DZP-level reorganization energies as low as 147 meV, rival or surpass the corresponding values for fullerenes, ITIC-OF, and ITIC-4F, and track a positive correlation between the ITIC-nF space-charge limited electron mobility and n. Finally, a heretofore unrecognized solution-phase redistribution process between the 2-(3-oxoindan-1-ylidene)-malononitrile-derived end-groups (EGs) of IDTT-based NFAs, i.e., EG(1)-IDTT-EG(1) + EG(2)-IDTT-EG(2) reversible arrow 2 EG(1)-IDTT-EG(2), with implications for the entire ITIC PSC field, is identified and mechanistically characterized, and the effects on PSC performance are assessed.