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 complex1a-BF2(n= 8) was determined by X-ray analysis; it crystallizes in theP1̄ triclinic space group and the geometry of boron atoms is tetrahedral. The crystal is considered to be linear-shaped with a length ofL∼ 33.92 Å. A relatively small dihedral angle ofca.3.30°-5.75° was observed between both neighboring phenyl groups and tetrahedral BF2moiety. Mesomorphic properties were crucially impacted by the structure of the terminal group. Ligands1a-bwere not mesogenic; however, both the series of1a-BF2and1b-BF2complexes formed SmC or/and N phases. The H-bonding interactions are attributed to the occurrence of mesomorphism in compounds1-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 atλmax= 445-466 nm in CH2Cl2. Compounds1a-BF2aggregated in higher water fractions (fw), which turned on their light emission process, whereas weak PL signals were recorded atfw< 50% because the luminogen was fully dissolved and quenched in these solvent compositions. The PL intensity was enhanced atfw> 60% until it reached the maximum intensity atfw∼ 90%. Thus, compound1a-BF2is AIE active.