The self-assembly of surfactants in aqueous solution can be modulated by the presence of additives including urea, which is a well-known protein denaturant and also present in physiological fluids and agricultural runoff. This study addresses the effects of urea on the structure of micelles formed in water by the fluorinated surfactant perfluoro-n-octanoic acid ammonium salt (PFOA). Analysis of small-angle neutron scattering (SANS) experiments and atomistic molecular dynamics (MD) simulations provide consensus strong evidence for the direct mechanism of urea action on micellization: urea helps solvate the hydrophobic micelle core by localizing at the surface of the core in the place of some water molecules. Consequently, urea decreases electrostatic interactions at the micelle shell, changes the micelle shape from prolate ellipsoid to sphere, and decreases the number of surfactant molecules associating in a micelle. These findings inform the interactions and behavior of surface active per- and polyfluoroalkyl substances (PFAS) released in the aqueous environment and biota.