Crystalline SnO2/reduced graphene oxide (RGO) nanocomposites were synthesized by a one-pot microwave-assisted non-aqueous sol–gel method, in which partially reduction of the graphene oxide and nanoparticle formation occurs simultaneously. Composite samples with different SnO2 loadings on the RGO were prepared and characterized by TEM, XRD, TGA-DSC and FT-IR. Chemoresistive devices, consisting of a thick layer of the samples synthesized on alumina substrates provided with Pt interdigitated electrodes, were fabricated and their electrical and NO2 sensing characteristics investigated. The results obtained have shown the possibility of a fine tuning of the sensing characteristics of the devices fabricated by simply controlling the amount of metal oxide nanoparticles loaded onto the reduced graphene oxide sheets. This was explained on the basis of the critical role played by the n-SnO2/p-RGO heterojunction formed on the composite materials.