Pieces of porous polycrystalline SnO2 with and without cobalt have been formed by the slip-casting method, using ceramic powders synthesized by the controlled precipitation method. A suitable␣methodology was developed for forming and sintering the pieces to enable controlled modification of their microstructure, principally grain size, porosity, and type of intergranular contacts. Better control of the microstructure was obtained in the samples containing cobalt. In these, predominance of open necks and intergranular contacts was observed, which can represent Schottky barriers. Because of its good structural homogeneity, porosity, and small grain size (of the order of 1 μm), the sample with 2 mol.% Co sintered at 1250°C for 2 h was selected for electrical characterization by complex impedance spectroscopy, varying the operating temperature, concentration and nature of the surrounding gas (air or CO), and bias voltage. The resulting R p and C p curves were very sensitive to variation in these parameters, being most obvious for the C p curves, which showed a phenomenon of low-frequency dispersion when bias voltages other than zero were used, in the presence of O2, and at operating temperature of 280°C. The electrical behavior of the SnO2 with 2 mol.% Co sample sintered at 1250°C was consistent with the nature and microstructural characteristics of the active material and was justified based on the presence of shallow- and deep-type defects, and variations in barrier height and width, caused by adsorption of gas molecules.