Metal oxide semiconductor (MOS) gas sensors show poor selectivity when exposed to mixed gases. This is a challenge in gas sensors and limits their wide applications. There is no efficient way to detect a specific gas when two homogeneous gases are concurrently exposed to sensing materials. The p-n nanojunction of xSnO2-yCr2O3 nanocomposites (NCs) are prepared and used as sensing materials (x/y shows the Sn/Cr molar ratio in the SnO2-Cr2O3 composite and is marked as SnxCry for simplicity). The gas sensing properties, crystal structure, morphology, and chemical states are characterized by employing an electrochemical workstation, an X-ray diffractometer, a transmission electron microscope, and an X-ray photoelectron spectrometer, respectively. The gas sensing results indicate that SnxCry NCs with x/y greater than 0.07 demonstrate a p-type behavior to both CO and H2, whereas the SnxCry NCs with x/y < 0.07 illustrate an n-type behavior to the aforementioned reduced gases. Interestingly, the SnxCry NCs with x/y = 0.07 show an n-type behavior to H2 but a p-type to CO. The effect of the operating temperature on the opposite sensing response of the fabricated sensors has been investigated. Most importantly, the mechanism of selectivity opposite sensing response is proposed using the aforementioned characterization techniques. This paper proposes a promising strategy to overcome the drawback of low selectivity of this type of sensor.