The addition of certain co-solvents to the hydrothermal synthesis starting solution can greatly alter morphology and enhance different morphology dependent properties of the synthesized material. While ethanol is the most common co-solvent used for the synthesis of various SnO2 nano/microstructures by hydro/solvothermal process, it is not clear how the use of some other alcoholic co-solvents (for example, methanol or isopropanol) affect morphology and properties of SnO2, especially if synthesis is done under similar conditions as in the case of ethanol co-solvent. In the present study, we investigated how the use of various alcoholic co-solvents (methanol, ethanol, 2-propanol, ethylene glycol and glycerol) affects crystal structure, morphology and specific surface area of the hydrothermally synthesized SnO2. Additionally, sensitivity towards 100 ppm ethanol of the synthesized materials was tested. The formation of nanoparticles, rod-cluster structures and spherical SnO2 structures were observed depending on the alcoholic co-solvent used. The highest sensitivity (~22 at 250 °C) showed the material that was synthesized in the presence of ethanol co-solvent.