Abstract In the presence of “inert” electrolytes (sodium fluoride, sulfate, carbonate, phosphate) there exists a range of temperatures and thiourea (TU) concentrations (low and high respectively) where two distinct condensed TU monolayers, totally devoid of anions, are observed. The two relevant molecular structures which are suggested rest on the analysis of the following data: (1) E-T-[TU] phase diagrams derived from capacitance measurements, (2) superficial excesses and molecular areas, (3) charge densities, (4) inhibition power, and (5) kinetics displayed by the various phase transitions involved. Anions like ClO − 4, NO − 3, ClO − 3 are only coadsorbed within the gas-like film of TU, with the result that the pure TU condensed regions are squeezed detectably. On the other hand, anions known to interact strongly with Hg (Cl −, Br −, I −, SCN −)_do coadsorb significantly at all potentials. However, pure TU films tend to reappear if the concentration of these anions is lowered sufficiently with respect to that of the surfactant.