The global environmental concerns and the escalating demand for energy, coupled with a steady progress in renewable energy technologies, are opening up new opportunities for the utilization of renewable energy resources. Electrodeposition is well known for depositing metals and metallic alloys at the industrial level, with a wide range of applications from large area surface treatments to most advanced electronic industries. Electrodeposition of semiconducting materials represents a new challenge, not only from the academic point of view, but also from the economic point of view, since this method presents interesting characteristics for large area, low cost and generally low temperature and soft processing of materials. In this presentation, we exploited alternated electrodeposition of some metals by E-ALD (Electrochemical Atomic Layer Deposition) to obtain thin films, controlling the growth of the structures at the nanometric level. In this presentation we will report the results for the electrodeposition of an entire p-n junction of semiconductors deposited by E-ALD technique. In this communication we present a structural study of these composite ultra-thin films by means of electrochemical operando SXRD experiment performed at ID03 in Grenoble. We also present the results of modified surfaces obtained by electrodeposition or new catalysts obtained from microwave assisted pyrolysis (MAP) of waste tires for direct alcohol fuel cells. A fundamental aim of material sciences is to reckon the relationship between the properties of a device, and the morphological and structural characteristics of the surface. Combining basic electrochemical techniques with spectroscopic, microscopic and structural techniques is crucial for characterizing the structure-activity relationship for many different Materials for Energy Applications.