The heterogeneous reaction of nitryl chloride (ClNO2) on the air-water surface plays a significant role in the chloride lifecycle. The air-water surface is ubiquitous on ice surfaces under supercooled conditions, affecting the uptake and heterogeneous reaction processes of trace gases. Previous studies suggest that ClNO2 is formed on Cl-doped ice surfaces following the N2O5 uptake. Herein, a distinctive heterogeneous reaction mechanism of ClNO2 is suggested on an air-water surface containing Cl under supercooled conditions using combined classic molecular dynamics (MD) and Born-Oppenheimer MD simulations. It is found that N2O5 dissociates into a NO2+ and NO3- ionic pair on the top air-water surface. In the top layer of the surface containing barely any Cl-, NO2+ proceeds through hydrolysis and produces H3O+ and HNO3. Thus, surface acidification appears because of H3O+ yields. With NO2+ diffusion to the deep layer of the surface, NO2+ reacts with Cl- and forms ClNO2. Note that ClNO2 formation competes with NO2+ hydrolysis, and the rate of ClNO2 formation is 27.7[Cl-] larger than that of NO2+ hydrolysis. Afterward, the reaction of ClNO2 with Cl- becomes barrierless with the catalysis by H3O+, which is not feasible on a neutral surface. Cl2 is thus generated and escapes into the atmosphere (low solubility of Cl2), contributing to the Cl radical. The proposed mechanism bolsters the current understanding of ClNO2's fate and its role in Cl chemistry in extremely cold environments like the Arctic and other high-latitude regions in wintertime.