Porous flower-like ZnO nanostructures have been synthesized by a template-free, economical hydrothermal method combined with subsequent calcination. Calcination of the precursors produced flower-like ZnO nanostructures, composed of interconnected porous ZnO nanosheets with high porosity resulting from the thermal decomposition of the as-prepared precursors, i.e., flower-like basic zinc carbonate (BZC). Moreover, the nanostructures have been characterized through X-ray diffraction, thermogravimetric-differential thermalgravimetric analysis, scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller N2 adsorption–desorption analyses. Compared with ZnO nanorods, the as-prepared porous flower-like ZnO nanostructures exhibit a good response and reversibility to some organic gas, such as ethanol and acetone. The sensor responses to 100 ppm ethanol and acetone are 21.8 and 16.8, respectively, at a working temperature of 320 °C. In addition, the sensors also exhibited a good response to 2-propanol and methanol, which indicate that these porous flower-like ZnO nanostructures are highly promising for applications of gas sensors.