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In this study, the concentration gradient inside evaporating binary sessile droplets of 30, 50, and 60 vol % tetrahydrofuran (THF)/water mixtures was investigated. The 5 μL THF/water droplets were evaporated on a transparent hydrophobic substrate. This is the first demonstration of local concentration mapping within an evaporating binary droplet utilizing the aggregation-induced emission material. During the first two evaporation stages of the binary droplet, the local concentration can be directly visualized by the change of fluorescence emission intensity. Time-resolved average and local concentrations can be estimated by using the pre-established function of fluorescence intensity versus water volume fraction.