A detailed experimental (SCXRD) and theoretical (PIXEL and QTAIM) investigation of the evolution of different supramolecular motifs formed via the presence of both C(sp²)/(sp³)–F groups in the crystal packing has been performed in a series of newly synthesized substituted benzanilides (containing “both” the fluorine and the trifluoromethyl group in the same molecule) along with previously reported similarly related crystal structures [CrystEngComm, 2008, 10, 54–67; CrystEngComm, 2012, 14, 1972–1989, CrystEngComm, 2013, 15, 3711–3733]. It was observed that the highest stabilized molecular motifs primarily consist of C(sp²)–H⋯F–C(sp²) H-bonds in preference to C(sp²)–H⋯F–C(sp³) H-bonds in the crystal. The motifs involving C(sp²)–H⋯F–C(sp²)/(sp³) H bonds were observed to be present over the entire distance range between 2.2 and 2.7 Å, albeit the difference in energies of stabilization involving fluorine atoms attached to sp² and sp³ carbon is not significant in molecular crystals. From QTAIM analysis, the C(sp²)/(sp³)–F⋯F–C(sp²)/(sp³) interactions were observed to be a closed shell in nature and provide local stabilization, indicating the formation of bonds, similar to weak hydrogen bonds observed in crystals.