The overall quality of multilayer thin films prepared by electrodeposition is strongly influenced by the surface and interface roughness which increases with the layer number. For that very reason the reliable analysis of the first few layers can be necessary. However, in depth profiling methods based on sputtering techniques the first layer is always found at the bottom of the sputtered crater. Since the depth resolution decreases during sputtering, the analysis of the first few layers are difficult. In order to circumvent this problem, we used reverse Secondary Neutral Mass Spectrometry (SNMS) depth profiling method for electrodeposited multilayered films. We prepared thin film samples in two ways. First, Co/Cu multilayer stacks were electrodeposited on Si/Cr/Cu substrates and SNMS depth profiling was carried out from the direction of the topmost layer. Secondly, elecrodeposited Co/Cu multilayer stacks were coated with a few microns thick Ni layer and detached from the Si substrate in order to study the film structure from the side of the substrate. Using this latter method, we were able to analyze the first and, probably, the most even layers of the thin film structure with high resolution.