The micellar solubilization of naphthalene from its saturated aqueous solutions using the biosurfactant rhamnolipid was studied. Using the NMR diffusion method, selective measurements of the self-diffusion coefficients of molecules of all components of the solution—naphthalene, rhamnolipid, and water—were carried out at various rhamnolipid concentrations from 0.06 to 100 g/L. Based on the results of diffusometry, the distribution of naphthalene molecules between the states free in solution and states bound by micelles was found. With an increase in the concentration of rhamnolipids, the proportion of bound naphthalene molecules increases from 50% at CRL = 2 g/L to 100% at CRL ≥ 50 g/L. The micelle-water partition coefficient Km and the molar solubilization ratio MSR were calculated.