The Ni-Me-P alloy coatings containing metal as alloying component (Me = Co, W) in a Ni-P amorphous matrix, were potentiostatically electrodeposited onto a polycrystalline Cu substrate. Deposition potential was established based on polarization curves of electrodeposition of Ni-Co-P, Ni-W-P and Ni-P alloy coatings. SEM, EDS, XRD and X-ray microanalysis methods, were applied for chemical and physical characterization of the obtained coatings. Linear analysis of Ni, Co and W distribution in the microregions of the appropriate alloy coating revealed that surface distribution of these elements is homogeneous what is due to a molecular mixing of the amorphous nickel matrix with the alloying components. It was found that the Ni-Co-P and Ni-W-P coatings have the amorphous structure like the Ni-P deposit and alloying components as Co or W are built-in into the appropriate coating in the amorphous form. The mechanism of the induced codeposition of these ternary Ni-Me-P coatings, has been discussed.