Unique gas-sensing properties of semiconducting hybrids that are mainly related to the heterogeneous interfaces have been considerably reported. However, the effect of heterogeneous interfaces on the gas-sensing properties is still unclear, which hinders the development of semiconducting hybrids in gas-sensing applications. In this work, SnO2-SnS2 hybrids were synthesized by the oxidation of SnS2 at 300 °C with different times and exhibited high response to NH3 at room temperature. With the increasing oxidation time, the relative concentration of interfacial Sn bonds, O-Sn-S, among the total Sn species of the SnO2-SnS2 hybrids increased first and then decreased. Interestingly, it can be found that the response of SnO2-SnS2 hybrids to NH3 at room temperature exhibited a strong dependence on the interfacial bonds. With more chemical bonds at the interface, the lower interface state density and the higher charge density of SnO2 led to more chemisorbed oxygen, resulting in a high response to NH3. Our results revealed the real roles of the heterogeneous interface in gas-sensing properties of hybrids and the importance of the interfacial bonds, which offers guidance for the material design to develop hybrid-based sensors.