Many studies have been carried out concerning the development of SO2 sensors to detect and avoid its health prejudicial effects. However, there is still a lack of reliable, high-speed-response sensors that work at room temperature. In this work, the segregation of Ni in the SnO2−NiO system is used to obtain a rapid SO2 sensor response. Segregation and its structure consequences were studied by electron dispersive spectroscopy, infrared spectroscopy, and high-resolution transmission electron microscopy in nanopowders of SnO2−NiO with different compositions prepared by a polymeric precursor method. The sensor activity of SnO2−1 mol % Ni was studied and a linear calibration curve was formed with a maximum limit response of 32 ppm SO2.