Studies of the processes of the electrodeposition of Co-W alloy coatings from citrate and gluconate solutions are based on several reasons, this is why these processes are of both theoretical and practical, technological, interest.  First, these coatings are, as a rule, nano-crystalline, thus having specific magnetic, mechanical and tribological properties. Next, the technology of their preparation is ecologically quite friendly, so,  as such this technology can be a safe alternative to the electrolytic chromium plating.  Still, a number of anomalies are specific (with the account of the modern theory of electrodeposition of alloys) for the processes discussed in the report.  One type of anomaly is due to the fact that the composition of the prepared coating cannot be predetermined on the base of polarization characteristics of components (Co and W reduction)[1].  The other one is caused by the dependence of the deposition rate (current yield) and some coating properties (e.g., microhardness) on the time of deposition after the electrolyte of a certain composition is prepared.  The report deals with the two types of anomalies with the account of the electrolytes used - citrate or gluconate ones. The methods applied are those traditional for the proteins chemistry: gel-chromatographic separation combined with the spectrophotomentry of the separation products and the determination of their electrochemical activity by cyclic voltammetry. It is demonstrated that the studied solutions are composed of a number of complexes (associates) with a high molecular mass (~1000 g/mol). It is established that solutions contain both individual complexes (associates) of Co and W and their mixtures.  It is shown than the reduction process up to the metal state takes place in Co and Co-W associates but not in W ones. It is evident that the composition of a coating depends on the rate of the process of reduction of Co and Co-W complexes. It is demonstrated that the composition of the formed associates also depends on the solution pH and on the kinetic peculiarities of their formation process, which, in the end, influences the variations of their deposition rates and mechanical properties.