Acetic acid sensing materials for environmental and related food quality control requiring high sensitivity and selectivity, and ppb-level detection limit, remain challenging. Double-shell ZnO hollow microspheres were prepared by a surfactant assisted template method, and the resultant gas sensor showed excellent acetic acid sensing performance. The sensor response reached 116 to 100 ppm acetic acid at 270°C with a short response time of 3.2 s. The relationship between acetic acid concentration and the response was established, and the detection limit reached 100 ppb. DFT theory computational results demonstrated the highest adsorption energy of the ZnO gas sensor to acetic acid among all tested gases, proving its high selectivity to acetic acid. Besides, the unique double-shell hollow structure with abundant oxygen vacancy and large surface area might be the other factors that gave rise to its excellent acetic acid gas sensing performance. Based on the gas sensor, a method for fast quantitative detection of acetic acid content in vinegar was developed. The linear relationship between sensor response and acetic acid gas concentration of vaporized white vinegar was established, and the acetic acid content in the vinegar can be quickly determined. The result proved our acetic acid sensor to be a promising candidate for practical applications.