A series of new β-ketoimines containing a ferrocene moiety and their BF2 complexes have been synthesized and structurally characterized. The solvatochromism of the β-ketoimines was studied, putting in evidence a redshift with increasing solvent polarity. This positive solvatochromism can be attributed to a more polarized excited state compared with the ground state, due to intramolecular charge transfer (ICT) transitions. The β-ketoimines exhibited weak emission, attributable to the excited-state intramolecular proton transfer (ESIPT) phenomenon. This ESIPT effect is suppressed upon restriction of the keto-enamine tautomerism, induced upon addition of BF3⋅OEt2, which afforded the related BF2 complexes, characterized by an enhancement of the fluorescence through the ICT effect. Both the β-ketoimines and BF2 complexes exhibited significant aggregation-induced emission behavior in mixtures of CH3CN/H2O, due to restriction of intramolecular rotation in the aggregated state. The frontier molecular orbital levels, ground- and excited-state dipole moments (μg and μe), and the origin of electronic absorption spectra were studied by time-dependent DFT calculations. The second-order nonlinear optical (NLO) properties were determined by the electric-field-induced second-harmonic generation technique. The μβ1907 values of the β-ketoimines increased upon the formation of the related BF2 complexes, mainly due to an enhancement of the ground-state dipole moment. The results presented here reveal that some of these novel compounds are excellent multifunctional candidates for NLO and luminescence applications. © 2021 Wiley-VCH GmbH