Cyclic voltammetry and square wave voltammetry have been used to investigate the transfer of highly hydrophilic ions, including anions and cations, by a simple two polarized interfaces setup. The expression of apparent half-wave potential has been established detailedly by virtue of theory of sampled-current voltammetry involving semi-infinite linear diffusion, which indicates that the property of coupled ion transfer reaction has an effect on the position of the voltammogram on the potential scale. Since the data obtained agree well with literature values, it seems convincing to determine the transfer energies of those highly hydrophilic ions which are very important and have not been reported yet. Then it has been demonstrated as a novel way in combination with sensitive and fast square wave voltammetry for determining the transfer Gibbs energy of complex ions such as miscellaneous inorganic ions.