To enhance the catalytic performance of H2SO4-catalyzed alkylation, various catalytic additives have drawn considerable attention. Herein, the effects of deep eutectic solvents additives (DESs) on catalytic performance and interfacial properties of H2SO4 alkylation were systematically investigated using experimental methods and molecular dynamics (MD) simulation. Experimental results indicate that DESs additives with the optimal concentration about 1.0 wt% can efficiently improve C8 selectivity and research octane number (RON) of alkylate. However, DESs additives contribute less to the quality of alkylate at low temperature and to the lifetime of H2SO4. MD results reveal that the phenyl molecules of DESs additives play a major role in enhancing interfacial properties of H2SO4 alkylation, including enlargement of interfacial thickness, promotion of isobutane relative solubility and diffusion to butene, which is probably the main reason for the better quality of alkylate. This work gives a good guideline for the design of novel DESs for H2SO4 alkylation.