A novel complex absorbent composed of polyethylene glycol 200 (PEG200) and ionic liquids (ILs) was prepared for the absorption of volatile organic compounds (VOCs) such as dichloromethane (DCM) and benzene. We prepared complex absorbents composed of [EMIM][Cl], [BMIM][Cl], [HMIM][Cl], [BMIM][BF4], [BMIM][PF6], [BMIM][NTF2], and PEG200, respectively, and studied the absorption properties of these six complex absorbents for DCM and benzene. The results show that under the optimized situation, the absorptivity of [HMIM][Cl]−PEG200 complex absorbent for DCM is 85.46% in the first 5 min, and 87.15% for benzene. No obvious decay in the absorptivity of [HMIM][Cl]−PEG200 for DCM and benzene was observed in five cycles, indicating an impressive regeneration performance. Furthermore, the mechanism of ionic liquid absorption for VOC is explored by thermodynamic analysis and quantum chemical calculations. The theoretical calculation results show that the [HMIM][Cl]−DCM interaction is stronger than the [HMIM][Cl]−benzene interaction, which is consistent with the results of the absorption experiment. Moreover, the strong hydrogen bonds can be formed between both [HMIM][Cl]−DCM and [HMIM][Cl]−benzene.