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 σCCex of X, and the substituent specific cross-interaction effect ΔσCCex2 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 ΔσCCex2 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.