Abstract: Effects of meta-substituent of 3,4'/4,3'/3,3'-substituted benzylideneanilines (XBAYs) on the electrochemical reduction potentials (E_(Red)) were investigated, in which 49 samples of target compounds were synthesized, and their reduction potentials were measured by cyclic voltammetry. The substituent effects on the E_(Red) of target compounds were analyzed and an optimality equation with four parameters (Hammett constant σ of X, Hammett constant σ of Y, excited-state substituent constant σ_CC^ex of X, and the substituent specific cross-interaction effect Δσ_CC^ex2 between X and Y) was obtained. The results show that the factors affecting the E_(Red) of 3,4'/4,3'/3,3'-substituted XBAYs are different from those of 4,4'-substituted XBAYs. For 3,4'/4,3'/3,3'-substituted XBAYs, σ(X) and σ(Y) must be employed, and the contribution of Δσ_CC^ex2 is important and not negligible. Compared with 4,4'-substituted XBAYs, X group contributes less to 3,4'/4,3'/3,3'-substituted XBAYs, while Y group contributes more to them. Additionally, it was observed that either para-substituted XBAYs or meta-substituted XBAYs, the substituent effects of X are larger than those of Y on the E_(Red) of substituted XBAYs.