The study about homojunctions and heterojunctions has scientific and technological value, because the mechanisms of formation and performance of these structures are not fully known. These junctions are in the base of different technologies, such as diodes, transistors, capacitors and supercapacitors, varistors, photovoltaic cells, detector of UV light, many kinds of sensors, catalysts and photocatalysts, among others. The present thesis aims to contribute to the development of polycrystalline ceramic systems (micro and nanostructured) based on ZnO and SnO2 and to the understanding ofthe mechanisms of formation of homojunctions and heterojunctions present in these systems and their relations with the varistor behavior, in terms of stability and degradation. Scanning electron microscopy, X-ray energy dispersive spectroscopy and X-ray diffraction were used to the microstructural characterization. Thermal and dilatometric analyses were used to determine the parameters and mechanisms of densification and sintering that give rise to the junctions considered. For the determination of the electrical characteristics, analysis of capacitance and polarization curves were used. Depending on the chemical compositions a variely of microstructures were obtained containing homojunctions and heterojunctions, with different densification levels and distinct varistors characteristics, that it, nonlinear behavior between voltage and electric current, with different magnitudes of switching voltages permitting to correlate the electrothermal behavior of varistors with the characteristics of homojunctions and heterojunctions considered.