The hydrophilic ionic liquid (IL) [EMIM][BF 4 ] was adopted to absorb two chlorinated volatile organic compounds (CVOCs), named 1,2dichloroethane and 1,1,2-trichloroethane. First, [EMIM][BF 4 ] was screened out as the optimal absorbent from 69 IL candidates by the COSMO-RS model. Then, CVOC absorption experiments were conducted usingshows the highest absorption rate for both 1,2dichloroethane (95.81%) and 1,1,2-trichloroethane (84.91%). Quantum chemical calculations show that both strong intermolecular electrostatic interaction and van der Waals interaction promote the absorption of CVOCs by [EMIM][BF 4 ]. Subsequently, industrial-scale CVOC capture processes, simulation and optimization, were carried out with [EMIM][BF 4 ] and TEG as absorbents, to attain the goal of reducing the concentration of CVOCs in the gas stream to 500 ppm (in mole fraction). The result shows that [EMIM][BF 4 ] has a higher processing capacity and a lower heat duty under optimal operating conditions.