Schiff bases have many chemical and biological applications in medicine and pharmaceuticals due to the presence of an imine group (-C=N-). These bases are used in many different fields of technology, and in photochemistry because of their photochromic properties. Here, the structural and electronic properties of the Schiff base formed by tacrine and saccharin (TacSac) were explored using density functional theory with the B3LYP, M06-2X, M06L, and omega B97XD functionals in combination with the 6-311++G(d,p) basis set. The time-dependent formalism was used at the B3LYP/6311++G(d, p) level to obtain electronic transitions. The calculations were repeated in an implicit solvent model mimicking water, using the polarizable continuum model in conjunction with a solvation model based on a density approach. The results indicate that TacSac cannot form spontaneously, but can be obtained in mild reactions. However, the resulting Schiff base displays different characteristics to its monomers. It also has the potential for use in photochemical intramolecular charge-transfer systems.