A SEM, DRS and XAS study was carried out on ultra-thin films with chemical composition belonging to the Cu-Zn-S ternary system, related to the kesterite-type materials, in the light of their potential application to thin film photovoltaic technology. The films, realized through the layer-by-layer E-ALD electrochemical technique, reveal variable phase composition as a function of the applied E-ALD sequence. In particular, by increasing the Zn cycles per Cu cycle from 1: 1 to 9: 1, the number of detected phases changes from 3 to 2. In all samples, Cu mainly crystallize in a Cu2S type phase, whereas Zn occurs as ZnS. In the 1: 1 sample, additional ZnO is detected. The variable phase composition parallels apparent changes in the sample morphology. In all samples, a sulphide thin film is covered by a net of elongated nanostructures, the length of which decreases with increasing the number of Zn cycles per Cu cycle. All these evidences are interpreted as due to the operating electrochemical route during the synthesis and confirm the lack of miscibility between Cu2S and ZnS, thermodynamically relevant after the E-ALD has stopped. The band gap values exhibited by the three films, modulated by changing the copper: zinc ratio, progressively approach a value useful for solar energy conversion, thus strongly proposing these new sulfide nanomaterials for photovoltaics and photochemical applications. (C) 2015 Elsevier Ltd. All rights reserved.