Rapid discovery of a deep eutectic solvent (DES) and its increasing application in various scientific applications demands a well-defined polarity scale for the new generation of eutectic solvents. The tunable nature of a DES facilitates to increase its number by combining various hydrogen bond acceptors and donors in multiple molar ratios. Therefore, the experimental measurement of polarity scale represented by solvatochromic parameters is a cumbersome task. In this context, we have developed a first-principle-based conductor-like screening model-real solvent (COSMO-RS)-derived predictive modeling approach to predict the Kamlet−Taft solvatochromic parameters of 26 hydrophilic and 62 hydrophobic DESs. The COSMO-RS-derived energies, that is, hydrogen bonding energy (E HB ), misfit energy (E MF ), and van der Waals energy (E VDW ), are linearly correlated with the experimental data set of 28 DESs having 4 choline chloride, 17 tetraalkylammonium organic salt, 4 menthol, and 3 betaine subclasses. A lowest root-mean-square deviation (rmsd) of 0.06% for the choline chloride class of DESs and a highest rmsd of 3.14% for the tetrabutylammonium chloride class of DESs are obtained. Therefore, the correlated models are then extended to develop 60 DESs consisting of 15 choline chloride DESs, 4 different hydrophilic DESs, 17 tetraalkylammonium organic salt origin DESs, 7 menthol DESs, and 17 thymol-based DESs.