In this paper, an acetone gas sensor based on a polyvinyl alcohol (PVA) self-assembled whispering gallery mode (WGM) microbottle resonator coated with polydimethylsiloxane (PDMS) is proposed and demonstrated. The preparation of the PVA self-assembled microresonator and the coating of PDMS are all finished by employing a dip coater. Compared with the PVA microresonator and the PDMS microresonator, the PVA microresonator coated with PDMS shows the highest acetone gas sensitivity, which is up to −6.34 pm/ppm. Besides, it can effectively reduce the effects of humidity on the detection of acetone gas compared to the PVA microresonator. Since the concentration of acetone in breathing gas is an indicator of diabetes, the proposed sensor with the benefits of small size, low cost, and simple manufacture using non-toxic materials presents promising applications for painless and non-invasive diagnosis of diabetes.