On the search of new design procedures for high performance catalysts we have obtained a very precisely defined surface architecture starting from a particular host structure. In this case, high purity La1−xCaxAl1−yNiyO3 (x = 0, 0.1; y = 0.1, 0.2, 0.3) perovskites were chosen, prepared by the citrate method and evaluated in the ethanol steam reforming reaction. The samples were characterized by X-ray diffraction (XRD), specific surface area measurements, X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge structure (XANES) and extended X-ray adsorption fine structure (EXAFS), temperature-programmed reduction (TPR) and Hydrogen Chemisorption. All the samples presented an excellent catalytic activity and stability. Exceptionall...