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,　[TEBAC][PhOH]　consisting　of　triethyl　benzyl　ammonium　chloride　(TEBAC)　and　phenol　(PhOH),　was　considered　as　the　most　suitable　absorbent.　Systems　with　[TEBAC][PhOH]　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　[TEBAC][PhOH]　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.　©　2023　The　Authors.　AIChE　Journal　published　by　Wiley　Periodicals　LLC　on　behalf　of　American　Institute　of　Chemical　Engineers.