This work aims to investigate the effect of liquid physical properties on the behavior of binary droplets impact on the heated smooth aluminum alloy plate with a high-speed imaging system. Two groups of mixed solutions with similar boiling point differences are selected as the working liquid, in which the low-boiling-point components are both ethanol and the high-boiling point components are propanol and water, respectively. Compared to the ethanol/propanol binary droplets, the experimental results show that the ethanol/water binary droplets have diverse impact phenomena and significantly broad transition boiling regimes, as well as the reduced droplet residence time and increased Leidenfrost temperature point. With the decreasing ethanol content in ethanol/water binary droplets, these effects become more prominent. For secondary atomization, the ethanol/water binary droplet undergoes parent droplet breakup into fragment droplets with larger diameters (Ds > 0.3 mm). Both binary droplets produce satellite droplets with small diameters (Ds < 0.3 mm) by puffing and ejection. In terms of the ethanol/propanol binary droplet impact, the probability of puffing is higher and the satellite droplet diameters are small. In the ethanol/water binary droplet impact, the probability of ejection is higher and the satellite droplet diameter distribution is wider. When an ethanol/water binary droplet of 25 vol.% ethanol content impacts the heated wall at Ts = 120 °C, a novel large bubble shrinkage phenomenon occurs at the late stage of droplet evaporation. This phenomenon is proposed to be relevant to the increasing surface tension and saturation temperature with decreasing ethanol content, as well as the decreasing ambient temperature above the top surface of the bubble.