Adsorption and activation for substrates and the stability of Pd species in Pd-based catalysts are imperative for their wider adoption in industrial and practical applications. However, the influence factor of these aspects has remained unclear. This indicates a need to understand the various perceptions of the structure–function relationship that exists between microstructure and catalytic performance. Herein, we revisit the catalytic performance of supported-ionic-liquid-phase stabilized Pd-based catalysts with nitrogen-containing ligands as a promoter for acetylene hydrochlorination, and try to figure out their regulation. We found that the absolute value of the differential energy, |E_ads(C₂H₂)-E_ads(HCl)|, is negative correlated with the stability of palladium catalysts. These findings imply that the optimization of the electron structure provides a new strategy for designing highly active yet durable Pd-based catalysts.