Although spraying antifreeze solution onto cold surface has been proven effective for frost inhibition, the freezing characteristics of alcohol binary droplet and the accompanying frosting behavior on freezing droplet surface remain unclear. Visualization experiments were carried out to achieve the freezing-frosting processes of ethylene glycol and glycerol solution droplets on cold surface under varying conditions. Experimental results demonstrate that alcohol droplet exhibits prolonged freezing duration and reduced deformation. The formation of an annular dry zone surrounding the droplet inhibits frost crystal propagation, increasing propagation time by 3–6.2 times. Different from water droplet, the freezing mechanism of alcohol droplet is attributed to frost crystal on the cold surface initiating nucleation upon contacts with the droplet. The solution membrane formed on the freezing droplet surface rises along the frost crystal inducing localized melting, which results in the frost crystals sparse and freezing droplet forming circular table-shaped morphology.