Drying of binary sessile droplets consisting of ethanol and octamethyltrisiloxane on a high-energy surface is investigated. During the process of evaporation, the droplets undergo liquid-liquid phase separation, resulting in the appearance of microdroplets at the liquid-air interface, which subsequently violently burst. This phase separation is attributed to water vapor transfer into the droplet, which modifies the solubility and leads to the formation of a ternary mixture. The newly formed ternary mixture may undergo nucleation and growth or spinodal decomposition, depending on the droplet composition path. By control of the relative humidity of air, phase separation can be mitigated or even eliminated. The droplets also display high mobility and complex wetting behavior due to phase separation, with two contracting and two spreading stages. The mass loss experiments reveal that the droplets undergo three distinct drying stages with an enhanced evaporation rate observed during the phase separation stage. A modified diffusion-limited model was employed to predict the evaporation rate, accounting for the physiochemical changes during evaporation and proved to be consistent with experimental observations. The findings of this work enhance our understanding of a coupled fundamental process involving the evaporation of multicomponent mixtures, wetting, and phase separation.