The effect of the substituents, solvent polarities and hydrogen ion concentration on the electronic structure and UV/VIS absorption spectra of some Schiff bases, derivatives of N-(R-benzylidene)benzidine (R = o-NO2and o-OH, p-OH) and N-(R-furfurylidene)benzidine (R = H and 5 - NO2), have been studied. The spectral shifts obtained in various organic solvents were discussed on the basis of the specific solute - solvent interactions through the formation of hydrogen bonds between hydrogen-bond donor (HBD) solvents and the benzidine nitrogen atom of the Schiff bases. Some interpretations of the electronic aspects of this type of hydrogen bonding were discussed as well as the stabilization effects due to the solvation. Finally, the pK values of the compounds were determined.