The aim of this paper is the presentation of the structure and Auger electron spectroscopy studies on the electrodeposited Ni-Mo alloys with different polymers. Composites based on Ni-Mo alloys with polytiophen, polypyrrole and polyethylene were obtained by electrochemical method. Depending on the potential and current density of electrodeposition and electropolymerization processes. The structural analysis made by X-ray diffraction shows that the solid solution of molybdenum in nickel is forming. The unit cell parameters of solid solution are slightly changing with the increasing of molybdenum contents in the alloy. The analysis of the diffraction line broadening indicates presence of the Ni-Mo solution nanocrystallites in the deposited layers. The Auger electron spectroscopy verifies both the presence of the solid solution of molybdenum in nickel and presence of polymers in composites. The SEM images show the general microstructure typical for the grain structure. Composites obtained by electrochemical method studied in this paper are unique in that the electrochemical methods can be used for processing ceramics, polymers, metals, composites and hybrid materials. The co deposition of alloys with polymers or polymerization with alloy decomposition have created new electrode materials for a number of applications including rechargeable batteries, electrochemical sensors etc.