Wetting and evaporation of droplets are ubiquitous and important to many industrial and domestic applications. While most of the research to date focuses on pure fluids, these are typically never alone; hence, understanding wetting and evaporation of binary mixtures is of much needed. In this work, we introduce the different wetting regimes as Cassie-Baxter, non-wetting Wenzel, and wetting Wenzel, which are function of the fluid concentration, i.e., the surface tension of the mixture, and the surface micro-pillar spacing, i.e., solid fraction. These wetting regimes are then supported by classical wetting theoretical equations. Moreover, when a liquid droplet is not in equilibrium with its vapour mass transfer via evaporation ensues with the associated heat removed from the droplet, the substrate and the surroundings due to evaporative cooling. The four typical evaporation behaviours reported in the literature, namely the constant contact radius, constant contact angle, mixed mode, and stick-slip, have been observed and reported. The different binary fluid composition coupled with the preferential evaporation of the most volatile fluid on the structured surfaces investigated, are then addressed providing a predictive framework for the evaporation mode at the initial stage of evaporation. For example, as the most volatile component evaporates the local surface tension of the droplet increases and the contact angle may increase in time, which further decreases the contact area of the droplet hindering the available area for heat transfer. We conclude that the initial evaporation mode, influencing both the mass and heat transfer dynamics during evaporation, is then governed by the initial wetting regime. Guidelines for the different initial wetting regimes and evaporation modes function of fluid surface tension and the surface structures underneath are here proposed contributing to the design of heat transfer, microfluidics and/or patterning applications.