The rapid interaction between o-tolidine and p-toluidine (pi-donors) with the pi-acceptors, e.g., 3,5-dinitrobenzoic acid (DNB) and 2,6-dichloroquinone-4-chloroimide (DCQ) results in the formation of 1:1 charge-transfer complexes as the final products, [(o-tolidine) (acceptor)] and [(p-toluidine) (acceptor)]. The final products of the reactions have been isolated and characterized using FTIR, 1HNMR spectroscopy and elemental analysis as well as photometric titration. The stoichiometry and apparent formation constants of the complexes formed were determined by applying the conventional spectrophotometric molar ratio method.