A computational method was developed which relates the empirical linear solvation energy relationship (LSER) solute polarity parameter, S (formerly denoted ), to two more fundamental quantities: a polarizability term and a computed solvent-accessible-surface electrostatic term. Electrostatics computations were conducted explicitly or with dielectric field polarizable continuum models (PCM, SCIPCM, IPCM), employing a density functional theory (B3LYP/6-311G(2df,2p)) or efficient Hartree−Fock (HF/MIDI!) method for 90 polar and nonpolar organic solutes. Electrostatic parameters calculated at electron isodensity solute surfaces were found to produce significantly better correlations with empirical S values than the same electrostatic parameters deduced from a fixed Bondi atomic radii based surface. The best-fit expression was found employing SCIPCM/IPCM at the 0.0004 e-/bohr3 solvent-accessible-surface: Sfit = 0.46E − 0.091ΣVs2, with squared correlation coefficient = 0.96 and standard deviation = 0.10, where E is a measured solute excess polarizability scale and ΣVs2 is a quantum-calculated solute electrostatic descriptor in kcal Å/mol. The resulting model is more accurate than previously developed estimation approaches and relies on only two fitted coefficients; it has the potential advantage of applicability to any solute composed of C, H, N, O, S, F, Cl, and Br. Finally, this investigation offers quantitative insight into the relative contributions of solute polarity and solute polarizability to the empirical LSER polarity parameter, S.