Electrolytic coatings of alloys on the base of iron subgroup elements with refractory metals, formed in gluconate solutions, are the best alternative for the currently widely used electrolytic chromium coatings, due to their specific functional properties [1]. However, the deposition process of such coatings is considered “anomalous” [2] and does not make it possible to form electrochemical coatings with the required composition and physical properties. Studies of the composition of gluconate electrolytes is of a special interest, since it allows for revealing the stages of the mechanism of the induced codeposition, with many potential outcomes. In order to study the composition of the gluconate electrolyte the method of gel-chromatographic separation was used, which permits to separate the electrolyte under study into its components ( complex compounds, associates, single chemical compounds, etc.), that can be extracted from the sample analyzed as a separation fraction. The fractions from the chromatographic column contain the separated electrolyte components, whose distribution on the base of molecular masses, in the outcoming eluent is inversely proportional to the volume of the passed eluent because chemical compounds with a higher molecular mass come out first [3]. The three-step separation of the gluconate electrolyte was carried out as depicted in Fig.1. The formation is demonstrated of complex compounds in the electrolyte with the molecular mass of >1000. It was found that the electrolyte is composed of a number of complex Co and W compounds, some of which contain only one of those metals as the central ion/ ions.