Structured, porous, and hollow tubular tin oxide (SnO2) and reduced graphene oxide (RGO) composites were synthesized through a combination of electrospinning and hydrothermal procedures. The morphology and structural features of the samples were analyzed and their sensing performance was tested. RGO/SnO2 composites exhibited a better sensing performance than SnO2. The optimum mass ratio of RGO in the composite was assessed as 1w%, leading to an excellent sensing response of 10.0–32.2ppm NO2 at a temperature of 150°C, approximately 10-fold that of SnO2. Thus, the enhancement of the gas sensing properties was attributed to the addition of RGO.