Hierarchical SnO2 blooming nanoflowers were successfully fabricated via a simple yet facile hydrothermal method with the help of different surfactants. Here we focus on exploring the promotion effects of surfactants on the self-assembly of 2D SnO2 nanosheets into 3D SnO2 flower-like structures as well as their gas-sensing performances. The polyporous flower-like SnO2 sensor exhibits excellent gas-sensing performances to ethanol and H2S gas due to high porosity when polyvinyl pyrrolidone is added into the precursor solution as a surfactant. The response/recovery times were about 5 s/8 s for 100 ppm ethanol and 4 s/20 s for 100 ppm H2S, respectively. Especially, the maximum response value of H2S is estimated to be 368 at 180 °C, which is one or two orders of magnitude higher than that of other test gases in this study. That indicates that the sensor fabricated with the help of polyvinyl pyrrolidone has good selectivity to H2S.