• The LLE data for water + diethylene glycol dimethyl ether + solvents were measured. • The distribution coefficient and separation factor were calculated. • The reliability of LLE data were verified by the Othmer-Tobias and Hand equations. • The NRTL and UNIQUAC models were applied to correlate the LLE data. • The binary interaction parameter values were obtained from the data correlation. Liquid-liquid equilibrium (LLE) data for water + diethylene glycol dimethyl ether + {methyl isobutyl carbinol, methyl isobutyl ketone, methyl isopropyl ketone, methyl tert -butyl ether, n -octanol and 2-ethyl-1-hexanol} was measured at 298.2 K under 101.3 kPa. The effect of separating diethylene glycol dimethyl ether from water is evaluated by the distribution coefficient and the separation coefficient. The Othmer-Tobias and Hand equations were chosen to examine the experimental LLE data. Meanwhile, the data was correlated by the NRTL and UNIQUAC thermodynamic models with AAD % less than 0.55 and RMSD % less than 0.77. The separation performance of six solvents was compared using the σ -profile analysis via the exploration of the intermolecular interaction. [ABSTRACT FROM AUTHOR]