On the basis of ab initio analysis of the calculation of impact of the cation composition tungstate-containing melt on structural peculiarities of EAP, the differences in the structure at implementation of sequential and simultaneous six-electron transfer are determined. According to the results of calculations of charge on the atoms of isolated tungstate-ion during transfer of 6 electrons in the electrode reaction on isolated tungstate-anion, the W atom is the only centre of electronic attack. At the electroreduction of cationised complexes, the electron charge is transferred to the cations and to the W atom, indicating the existence of two centres of electronic attack.