We report on a kinetic study for the nucleophilic addition reactions of diethyl 4-X-substituted benzylidenemalonates 1a-c (X = N(CH3)2, OCH3 and CH3) with N-nucleophiles, such as morpholine 2a, piperidine 2b and pyrrolidine 2c by UV–vis spectroscopy in acetonitrile solution at 20 °C. The Hammett plots demonstrate much better linear correlations with σp+ constants than with σp constants. These results are best interpreted in terms of ground state stabilization through resonance interactions between the electron-donating substituent and the CO2Et group. The effect of amine basicity on the reaction rate was examined quantitatively, leading to linear correlations with high βnuc values in the 0.82–0.93 range. The origin of the abnormally high βnuc values was interpreted in terms of dimer mechanism. Finally, with the help of our new proposed linear free energy relationship log k1K (20 °C) = sN (E + N) + log K, the stability of the dimer amines (K) have been evaluated from the measured apparent second-order rate constant (k1K) and the previously reported E, N and sN parameters of the employed electrophiles 1a-c and nucleophiles 2a-c. Additionally, a complementary theoretical study utilizing Density Functional Theory (DFT) with the B3LYP/6-311g(d,p) method was conducted in acetonitrile. An attempt is made to establish the correlation between equilibrium constant and stabilization energy the studied systems.