The development of reverse osmosis (RO) technology is still hindered by many obstacles, especially the low water permeance of RO membrane. Herein, an interfacial polymerization regulated by N-acyl imidazole chemistry was proposed to fabricate high permeance RO membranes. The improvement of membrane performance was achieved by simply adding 2-Methylimidazole (Hmim) into aqueous phase. More angstrom-scale free volume elements, which acted as water molecule transport channels, were formed in the polyamide separation layer due to the reaction and hydrolysis of Hmim. As a result, a substantial increase in water permeance was achieved while maintaining high NaCl rejection. In addition, more carboxylic acid groups were formed on the membrane surface due to the hydrolysis of N-acyl imidazole, thereby imparting higher hydrophilicity and anti-fouling properties to the membrane. With the addition of 1.5 w/w% Hmim, the water permeance of the prepared RO membrane was improved to 4.4 L m−2 h−1 bar−1, nearly 4.5 times compared to the control group, while maintaining a high NaCl rejection of above 98 %, thus successfully overcoming the permeability-selectivity trade-off limit. This work paves a new idea for the development of additives in the preparation of RO membranes.