AbstractWaterborne novolac epoxy based thermal resistant and fire‐retardant thermal insulation coatings were developed in this work. Novolac (phenolic) epoxy emulsion (PEE) was prepared by the phase inversion method based on formulation optimization by orthogonal array testing. The prepared emulsions have similar particle size, viscosity, and stability to commercial bisphenol a glycidyl ether epoxy emulsion (PZ). DSC results showed that the varnish film based on PEE had a higher glass transition temperature and initial thermal decomposition temperature compared with PZ cured by the same curing agent. Waterborne thermal insulation coating with PEE and PZ as binders and hollow glass microspheres (HGMs) as thermal insulation fillers were studied. The results indicated that the thermal conductivity of the coating decreased with an increase in HGMs content. Specifically, the thermal conductivity of the PEE coating containing 20 wt% HGMs is as low as 0.093 W/(m·K). It reduces the exterior temperature of the hot tank from approximately 200 °C to approximately 106 °C. Furthermore, the HGMs/PEE waterborne thermal insulation coating exhibits good thermal stability and flame retardance.