Icing of surfaces has become a serious issue, and effective methods for preventing ice accretion have received much attention in recent years. Here, a solvent volatilization-induced cross-linking hydroxy-terminated dimethylsiloxane (Si–OH) coating with tetramethoxysilane (TMOS) as a cross-linker is proposed for large-scale deicing applications. Interfacial adhesion tests and shear force analysis were conducted to confirm the large-scale deicing properties of the polydimethylsiloxane (PDMS) coating. Through characterization of morphology, it was found that there were negative correlations between roughness and constant shear force and shear strength. The mean constant shear force per unit width could be lower than 14 N/cm when the roughness was in the highest range fabricated in this research. In addition to the morphology of the surface, the mass ratio of the cross-linker to the premonomer affected the state of the surface and the deicing properties. When the mass ratio was lowered, uncross-linked molecular chains of the premonomer existed on the surface, which resulted in an increase in interfacial toughness and a reduction in shear strength. Finally, durability tests showed that the coating had excellent durability and could endure at least 50 cycles without an apparent increase in the constant shear force.