Different morphologies hierarchical flower-like tin dioxide (SnO2) nanostructures were fabricated by changing the volume ratio of glycol and de-ionized water (Vg:Vw=0, 1:2, 1:1 and 2:1) under a template-free and low-cost hydrothermal method and subsequent calcinations. The architectures, morphologies and gas sensing performances of the products were characterized by X-ray diffraction patterns (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) and gas-sensing measurement device. It can be observed that all the nanoflowers were composed of two-dimensional (2D) nanosheets, and the thickness of nanosheets is only about 9nm when Vg:Vw=1:1. The sensor based on the product of Vg:Vw=1:1 exhibited excellent gas sensing performance toward 500ppm acetic acid at 260°C, and the response value of this sensor was about 153.6, which was above 7.5 times higher than that of ammonia (about 20.3). In addition, the 3D flower-like SnO2 nanostructures exhibited not only high response and selectivity to ppm level acetone, but also fast response and recovery time within 10s, demonstrating it can be used as a potential candidate for detecting acetic acid. Finally, the possible formation mechanism was proposed, too.