The suitability of phenyl‐based deep eutectic solvents (DESs) as absorbents for toluene absorption was investigated by means of thermodynamic modeling and molecular dynamics (MD). The thermodynamic models perturbed‐chain statistical associating fluid theory (PC‐SAFT) and conductor‐like screening model for real solvents (COSMO‐RS) were used to predict the vapor–liquid equilibrium of DES–toluene systems. PC‐SAFT yielded quantitative results even without using any binary fitting parameters. Among the five DESs studied in this work, TEBACPhOH consisting of triethyl benzyl ammonium chloride (TEBAC) and phenol (PhOH), was considered as the most suitable absorbent. Systems with TEBACPhOH had lowest equilibrium pressures of the considered DES–toluene mixtures, the best thermodynamic characteristics (i.e., Henry's law constant, excess enthalpy, Gibbs free energy of solvation of toluene), and the highest self‐diffusion coefficient of toluene. The molecular‐level mechanism was explored by MD simulations, indicating that TEBACPhOH has the strongest interaction of DES–toluene compared to the other DESs under study. This work provides guidance to rationally design novel DESs for efficient aromatic volatile organic compounds absorption.