The advent of next-generation nonfullerene acceptors (NFAs) has propelled major advances in organic solar cells (OSCs). Here we report an NFA design incorporating CF 3terminated side chains having varying N-(CH 2 ) n -CF 3 linker lengths (n = 1, 2, and 3) which introduce new intermolecular interactions, hence strong modulation of the photovoltaic response. We report a systematic comparison and contrast characterization of this NFA series with a comprehensive set of chemical/physical techniques versus the heavily studied third-generation NFA, Y6, revealing distinctive and beneficial properties of this new NFA series. Singlecrystal diffraction analyses reveal unusual two-dimensional meshlike crystal structures, featuring strong interactions between the side chain CF 3 -terminal and NFA core F substituents. These atomistic and morphological features contribute to enhanced charge mobility and significantly enhanced photovoltaic performance. We show that varying the CF 3 -terminated side chain linker length strongly modulates light harvesting efficiency as well as charge recombination and the photovoltaic bandgap. The CF 3 -(CH 2 ) 2 -based OSC demonstrates the most balanced performance metrics, achieving a remarkable 19.08% power conversion efficiency and an exceptional 80.09% fill-factor. These results imply that introducing CF 3 -terminated side chains into other OSC conjugated constituents may accelerate next-generation solar cell development.