At present, the complex dispersed oxide systems Al2O3–Fe2O3 and Al2O3–TiO2 are the basis for creation of new ceramic and composite materials with improved functional properties. Thus, such mixed oxide systems and materials are widely used in various fields of modern industry, especially as heterogeneous catalysts and effective sorbents and agents in water and wastewater treatment. For example, composites and nanocomposites, based on the oxide system Al2O3–Fe2O3 are used to reduce and remove various ions - phosphate, bromate, Ni2+, NH4+, Cr6+, Hg2+. Besides, these materials exhibit catalytic activity and selectivity in the oxidation and decomposition reactions of different organic pollutants. At present, the main methods for the synthesis of such complex oxide systems are mechanochemical and chemical methods. We suggest to use an electrochemical method, based on the anodic dissolution of hybrid iron - aluminum and titanium-aluminum electrodes in aqueous solutions containing halide ions (F-, Cl-), to produce nanosized oxide systems Al2O3–Fe2O3 and Al2O3–TiO2. Compared with traditional methods electrochemical synthesis allows to adjust phase composition, as well as to obtain more uniform size of nanometer-sized particles. For example, size of particles (oxide systems Al2O3–Fe2O3) synthesized by us is not more than 100 nm and remains in this range after the high-temperature heat treatment (chemically obtained particles often have micron size and particle size range is essentially more). Also, in present paper relationships between parameters of electrochemical processes and the characteristics of the synthesized oxide system have been established. The influence of electrolysis mode (direct and alternating current), the composition of the solution, the current density, the ratio of the working surface area of the metal components on the intensity of dissolution of the hybrid electrode (Al-Fe, Al-Ti), and the characteristics of the synthesized oxide system have been shown. The optimal conditions of the hybrid electrode ionization have been experimentally established, and also the control parameters of conjugate anodic dissolution of two electrically contacting metals have been revealed. In this way, the combined anodic dissolution in the test aqueous media and subsequent heat treatment of the precipitates allows to obtain precursors of highly dispersed oxide systems Al2O3–Fe2O3 and Al2O3–TiO2. These results were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM).