The electrolytic deposition of an electropositive metal is often accompanied by electroless deposition. However, this process is very difficult to control. For that reason, our study has been aimed at the conditions of the electroless deposition of copper coating onto the iron powder particles front sulphate electrolyte. The process consists of two partial reactions: solid iron substrate dissolves into the solution, thus providing the electrons necessary for reduction of copper. The course of the electroless process depends to a large extent on the composition and pH of the electrolyte as well as on the size and concentration of the iron powder particles in the electrolyte. In order to suppress the spontaneous electroless deposition of copper, sodium citrate as complexing agent was used The following parameters were determined to characterize the reaction course: the heterogeneous rate constant of Fe powder dissolution and degree of Fe conversion as well as thickness of the Cu lover on the Fe powder, both of the latter evaluated upon attaining the stationary state. The main influence exhibited on the reaction course is the efficient surface area available for electroless deposition.