Materials with an artificial layered structure, also known as multilayers, have generated interest recently because of their unique properties. In this study, the electrolytic synthesis of NiP/Sn multilayers was attempted. Such an alternation of soft and hard sublayers mag improve the wear properties. The effect of plating-bath chemistry and current density on the microstructure was studied. Electrochemical measurements were performed to investigate the electrocrystallization of NiP on tin and vice versa. For the structural characterization scanning electron microscopy, coupled with microanalysis, and Rutherford backscattering spectroscopy were used. The potentiality and limitation of electrolysis as a process to produce compositionally modulated multilayers of small wavelengths are reported.