Herein, we report the synthesis of two new families of borondifluoride complexes derived from aroylhydrazines and the investigation of their mesomorphic and AIE properties. The crystallographic structure of the mesogenic complex 1a-BF₂ (n = 8) was determined by X-ray analysis; it crystallizes in the P triclinic space group and the geometry of boron atoms is tetrahedral. The crystal is considered to be linear-shaped with a length of L ∼ 33.92 Å. A relatively small dihedral angle of ca. 3.30°–5.75° was observed between both neighboring phenyl groups and tetrahedral BF₂ moiety. Mesomorphic properties were crucially impacted by the structure of the terminal group. Ligands 1a–b were not mesogenic; however, both the series of 1a-BF₂ and 1b-BF₂ complexes formed SmC or/and N phases. The H-bonding interactions are attributed to the occurrence of mesomorphism in compounds 1-BF₂, which was supported by FT-IR spectroscopy. The optical property of the boron complexes is related to their molecular structures, and they emitted blue-to-green emissions at λ_max = 445–466 nm in CH₂Cl₂. Compounds 1a-BF₂ aggregated in higher water fractions (f_w), which turned on their light emission process, whereas weak PL signals were recorded at f_w < 50% because the luminogen was fully dissolved and quenched in these solvent compositions. The PL intensity was enhanced at f_w > 60% until it reached the maximum intensity at f_w ∼ 90%. Thus, compound 1a-BF₂ is AIE active.