1,5-Dimethoxynaphthalene (1,5-DMN) and 2,3-DMN were synthesized using the phase transfer catalysis (PTC) technique. Their fluorescence is quenched by 7,7,8,8-tetracyanoquinonedimethane (TCNQ), picric acid, chloranil and bromanil. The quenching rate constant values k q were estimated. It was found that the rate of quenching of 2,3-DMN is slower than that of 1,5-DMN by the same acceptors. The role of the solvent polarity on the efficiency of fluorescence quenching of 1,5-DMN with picric acid was also studied. Spectral studies show that 2,3-DMN forms 1 : 1 charge transfer complexes (CTCs) with different π-acceptors in dichloromethane, while 1,5-DMN forms contact CTCs with TCNQ, chloranil and bromanil and 1 : 1 CTCs with tetracyanoethylene (TCNE) and picric acid. The equilibrium constants and thermodynamic standard reaction quantities of the CTCs were estimated.