The nucleophilic substitution reactions of p-substituted benzyl bromide with l-substituted N,N-dimethylanilines in methanol and acetonitrile binary solvent mixture which is known to an isodielectric solvent system kinetically and the results are as follows. The positive charge is developed on the reaction center of the substrate and it means that the bond cleavage is preceded more than bond formation in the transition state on the analogy of Hammett px values. The bond form3tlon is not progressed in the case of electron donating substituent of substrate. However, the bond formation is much developed in the case of electron withdrawing substituent of substrate on the analogy of Hammett py values. The nucleophilic attacking ability is shown a highest at 80% (V/V) methanol content and the bond formation is well progressed at the same methanol composition on the result of a cross interaction coefficient, pxy. The result of transition state structure that is applicated to the potential energy surface model is in accord with the result that Is applicated to the reaction susceptibilities. The reaction Is subject to the polarity-polarizability term more than the hydrogen bond donor acidity term by application to the solvatochromic parameter eouation.