We experimentally investigated the evaporation dynamics of acoustically levitated Ouzo droplets (a mixture of ethanol, water, and anise oil). Acoustic levitation has gained significant attention in various fields owing to its potential to create a lab-in-a-drop. Although evaporation is a key process in nature and industry, many studies have focused on single and binary components, and ternary droplets in acoustic levitation have rarely been experimentally investigated. In this study, the evaporation-induced spontaneous emulsification (the Ouzo effect) and phase separation process at 40–90 vol. % ethanol were visualized. We estimated the concentration change by evaporation of each component in the levitated ternary droplets based on an evaporation model to determine the experimental results. Our experimental results revealed four distinct stages of evaporation in levitated Ouzo droplets: (1) preferential evaporation of the volatile component (ethanol), (2) spontaneous emulsification (myriad micro-oil droplets generation), (3) phase separation forming a core–shell droplet, and (4) water evaporation completion resulting in the remaining oil droplets. Finally, we analyzed the emulsification process using a spacetime diagram. These findings suggest that acoustic levitation is suitable for physicochemical manipulation in mid-air.