Three novel ((4-(benzyloxy)benzylidene)amino)phenol compounds are synthesized and characterized. The electronic structures of the molecules have been investigated by using both experimental and theoretical methods. Kamlet–Taft and Catalan models are used to determinate the contribution of each solute–solvent interaction type. Schiff bases can be used as solvatochromic materials. Experimental ground and excited state electric dipole moments have been determined by using the Bilot–Kawski, Lippert–Mataga, Bakshiev and Kawski–Chamma–Viallet theories. The excited state dipole moment of (E)-2-((4-(benzyloxy)benzylidene)amino)phenol is estimated to be 38.809 times higher than the ground state dipole moment. The electronic absorption spectra, frontier molecular orbitals (HOMO and LUMO), molecular electrostatic potential and solvent accessibility surface of these compounds have been calculated by using the DFT (B3LYP)/6-311++G (d,p) theory and method. In addition, theoretical electronic transitions have been calculated by the B3LYP/6-311++G (d,p) and CAM-B3LYP/6-311++G (d,p) levels of theory. The (E)-2-((4-(benzyloxy)benzylidene)amino)phenol molecule is found to have the greatest semiconductor character.