With the ever-increasing laser power and repetition rate, thermal control of laser media is becoming increasingly important. Except for widely used air cooling or a bonded heat sink, water cooling of a laser medium is more effective in removing waste heat. However, how to protect deliquescent laser media from water erosion is a challenging issue. Here, novel waterproof coatings were proposed to shield Nd:Glass from water erosion. After clarifying the dependence of the waterproof property of single layers on their microstructures and pore characteristics, nanocomposites that dope SiO2 in HfO2 were synthesized using an ion-assisted co-evaporation process to solve the issue of a lack of a high-index material that simultaneously has a dense amorphous microstructure and wide bandgap. Hf0.7Si0.3O2/SiO2 multifunctional coatings were finally shown to possess an excellent waterproof property, high laser-induced damage threshold (LIDT) and good spectral performance, which can be used as the enabling components for thermal control in high-power laser cavities.