The application of metal oxide-based sensors for the detection of volatile organic compounds is restricted because of their high operating temperatures and poor gas sensing selectivity. Driven by this fact, we report the low operating temperature and high performance of C3H7OH and C2H5OH sensors. The sensors comprising SnO2 hollow spheres, nanoparticles, nanorods, and fishbones with tunable morphologies were synthesized with a simple hydrothermal one-pot method. The SnO2 hollow spheres demonstrated the highest sensing response (resistance ratio of 20) toward C3H7OH at low operating temperatures (75 °C) compared to other tested interference vapors and gases, such as C3H5O, C2H5OH, CO, NH3, CH4, and NO2. This improved response can be associated with the higher surface area and intrinsic point defects. At a higher operating temperature of 150 °C, a response of 28 was witnessed for SnO2 nanorods. A response of 59 was observed for SnO2 nanoparticle-based sensor toward C2H5OH at 150 °C. This variation in the optimal temperature with respect to variations in the sensor morphology implies that the vapor selectivity and sensitivity are morphology-dependent. The relation between the intrinsic sensing performance and vapor selectivity originated from the nonstoichiometry of SnO2, which resulted in excess oxygen vacancies (VO) and higher surface areas. This characteristic played a vital role in the enhancement of the target gas absorptivity and the charge transfer capability of SnO2 hollow sphere-based sensor.