Aqueous-phase processing of methylglyoxal (MG) has been suggested to play a key role in the formation of secondary organic aerosols and catalyze particle growth in the atmosphere. However, the details of these processes remain speculative owing to the lack of a complete description of the physicochemical behavior of MG on atmospheric aerosols. Here, the solvation and hydrolysis of MG at the air/liquid water interface is studied via classical and first-principles molecular dynamics simulations combined with free-energy methods. Our results reveal that the polarity of the water solvent catalyzed the trans-to-cis isomerization of MG at the air/liquid water interface relative to the gas phase. Despite the presence of a hydrophobic group, MG often solvates with both the ketone and methyl groups parallel to the water interface. Analysis of the instantaneous water surface reveals that when MG is in the trans state, the methyl group repels interfacial water to maintain the planarity of the molecule, indicating that lateral and temporal inhomogeneities of interfacial environments are important for fully characterizing the solvation of MG. The counterintuitive behavior of the hydrophobic group is ascribed to a tendency to maximize the number of hydrogen bonds between MG and interfacial water while minimizing the torsional free energy. This drives MG hydration, and our simulations indicate that the formation of MG diol is catalyzed at the air/liquid water interface compared to the gas phase and occurs through nucleophilic attack of water on the carbonyl carbon.