Direct observations of electrostatic potential variations along the flux surfaces of the TJ-II stellarator are presented. Measurements taken with two distant Langmuir probe arrays show differences in the edge floating potentials profiles of several tens of volts in electron-root wave-heated plasmas. The differences are reduced for higher densities and lower electron temperatures after the ion-root electric field forms at the plasma edge. Neoclassical Monte Carlo simulations estimate the correct order of magnitude for the overall variation in potential and predict the trend observed with the radial electric field. However, for the specific location of the probes, the simulations give differences smaller than those observed experimentally.