The effect of cationic, anionic and nonionic surface active additives, organic compounds and polymers on the electrodeposition of Zn-Mo coatings on steel substrate and detailed characterization in chosen optimal conditions was studied. The influence of polyethylene glycol (PEG) various concentration, sodium dodecyl sulphate (SDS), triton X-100, d-sorbitol, cetyl trimethyl ammonium bromide (CTAB), thiourea and disodium ethylenediaminetetraacetate (EDTA) on the electrodeposition process was examined. The composition of deposits was defined by wavelength dispersive X-ray fluorescence spectrometry (WDXRF). Results has shown that the current efficiency of the electrodeposition of Zn-Mo coatings is 71.4%, 70.7%, 66.7% for 1.5 g/dm3 PEG 20000, 0.1 g/dm3 Triton X-100 and 0.75 M D-sorbitol respectively. The surface topography and roughness of selected coatings on steel was investigated by atomic force microscopy (AFM). The attendance of D-sorbitol of 0.75 M in the solution cause clear reduction of grain size and the value of roughness parameter (Ra) in relation to SDS, PEG, Triton X-100 and the sample prepared without the additives. The morphology of electrodeposited layers was studied by scanning electron microscopy (SEM). The addition of selected additives to the electrolytic bath results in the formation of smoother, brighter and more compact Zn-Mo coatings in comparison to layers obtained from similar electrolytes but without the addition of surfactants. The optimal concentration of the most effective additives such as PEG 20000, Triton X-100 and D-sorbitol is 1.5 g/dm3, 0.1 g/dm3, 0.75 M respectively.