Mixed oxides of copper and aluminum were prepared in porous form by the citrate process under various calcination conditions. The oxide samples were characterized by several techniques to determine chemical structure and texture. Atomic absorption spectroscopy provided the fractions of copper soluble and insoluble in hot nitric acid, which closely corresponded to CuO and CuAl2O4, respectively. X‐ray diffraction (XRD) provided complementary information about the content of the pure and compound oxides. X‐ray line broadening, scanning electron microscopy, and transmission electron microscopy were used to estimate the size of crystallites or phase domains. The reduction by hydrogen of samples containing different amounts of CuO and CuAl2O4was studied by thermogravimetric analysis and XRD. The compound oxide CuAl2O4and part of CuO closely associated with Al2O3were reduced much more slowly than bulk CuO. Oxides of 1+ oxidation state, Cu2O and CuAlO2, were identified as reduction intermedia