Surfactant aggregation plays an important role in a variety of chemical and biological nanoscale processes. On a larger scale, using small amounts of amphiphiles compared to large volumes of bulk-phase modifiers can improve the efficiency and reduce the environmental impact of many chemical and industrial processes. To model ternary mixtures of polar, nonpolar, and amphiphilic molecules, we develop a molecular thermodynamic theory for polydisperse water-in-oil (W/O) droplet-type microemulsions and reverse micelles based on global minimization of the Gibbs free energy of the system. The incorporation of size polydispersity into the theoretical formulation has a significant effect on the Gibbs free energy landscape and allows us to accurately predict micelle size distributions and micelle size variation with composition. Results are presented for two sample ionic surfactant/water/oil systems and compared with experimental data. By predicting the structural and compositional characteristics of w/o microemulsions, the molecular thermodynamic approach provides an important bridge between the modeling of ternary systems at the molecular and the macroscopic level.