Sensors based on metal oxide semiconductors have been widely applied for the detection of several volatile organic compounds (VOCs). However, the development of sensing materials with high selectivity, improved sensitivity, low detection limit is still a challenge. In this work, bicone-like ZnO structure was synthesized by a rapid template-free microwave-assisted hydrothermal method and then applied as VOC sensor. The VOC-sensing tests revealed that ZnO structure presented a higher response toward butanone than to other VOCs, such as benzene, toluene, m-xylene, acetone, ethanol, acetaldehyde, and isopropanol. Moreover, the ZnO-based sensor showed an enhanced butanone-sensing performance at 400°C, including a response of 29.4-100 ppm of butanone, high sensitivity to detect low butanone concentration (2 ppm), and a low detection limit of 0.41 ppm. Therefore, the unique bicone-like ZnO structure might be a promising candidate for butanone sensors.