<p>Electronic properties of active sites profoundly influence catalytic production of value-added chemicals; however, rational description and modulation is still a significant challenge. Herein, we propose an effective metal-ion-chelation strategy guided by density functional theory prediction and in situ Raman observation to structurally tailor and quantitatively correlate the electronic properties of active sites in ionic liquid. Comprehensive characterizations and theoretical calculations, in combination with electronic properties–performance correlations, reveal the electronic peculiarity of nitrogen and oxygen centers can be controllably restructured for remarkable improvement of catalytic performance at near-ambient condition. The turnover frequency is increased by two folds with deactivation rate suppressed by more than one half, while the kilogram-scaled recycling pilot achieves similar performance for the probe methacrolein synthesis. This strategy further exhibits excellent applicability and tolerance in other substrates with representative functional groups. Our work expresses the significance of electronic properties and provides a valid regulation approach for ionic liquid catalysis.</p>