The surface affinity of tetramethylammonium iodide (TMAI) in aqueous solutions is investigated by surface tension measurements and molecular dynamics computer simulations. Experiments, performed in the entire composition range of solubility using the pendant drop method with two different setups, clearly reveal that TMAI is a weakly capillary active salt. Computer simulations performed with the AMBER force field reproduce the experimental data very well, while two other major force fields (i.e., CHARMM and OPLS) can still reproduce the experimental trend qualitatively; however, even qualitative reproduction of the experimental trend requires scaling down the ion charges according to the Leontyev-Stuchebrukhov correction. On the other hand, the GROMOS force field fails in reproducing the experimentally confirmed capillary activity of TMAI. Molecular dynamics simulation results show that, among the two ions, iodide has a clearly larger surface affinity than tetramethylammonium (TMA+). Further, the adsorption of the I- anions is strictly limited to the first molecular layer beneath the liquid-vapor interface, which is followed by several layers of their depletion. On the other hand, the net negative charge of the surface layer, caused by the excess amount of I- with respect to TMA+, is compensated by a diffuse layer of adsorbed TMA+ cations, extending to or beyond the fourth molecular layer beneath the liquid surface.