Deep eutectic solvents (DESs) emerge as a medium to enhance the depolymerization of lignin. One critical question is how the solvation of lignin in DESs may affect the reactivity of lignin. To shed light on this question, we investigate the solvation of four lignin dimers in three DES solutions using molecular dynamics simulations and quantum mechanical calculations. The four lignin dimers are composed of guaiacyl and syringyl units and are used as the models for lignin. The three DES solutions are composed of choline, Cl- and three acids: lactic acid, levulinic acid and oxalic acid. We investigate the preferential accumulation of individual DES components in the solvation shells and the exposure area and electrostatic potential of the β-O-4 linkage of the four lignin dimers in the three DESs. The results show that DESs could influence the affinity and nucleophilicity of the β-O-4 linkage through three effects: (1) forming a charged solvation shell, (2) varying the exposure of the β-O-4 linkage and (3) adjusting the electrostatic potential of the β-O-4 linkage. Our simulations indicate a comprehensive and multiscale effect of DESs on lignin decomposition.