New types of ceramic coatings based on SiO₂-Na₂O-B₂O₃-TiO₂ oxide phases were investigated as protection for boiler steel in power generation systems. Low-alloyed Cr-Mo 16Mo3 steel was coated with different compositions of enamel coatings to assess the protective potential of these coatings under water vapor at high temperatures. Oxidation at 650 °C for 50 h in Ar + water vapor was performed in a TGA apparatus to investigate the oxidation kinetics. The results indicate that the ceramic coatings provided a high degree of protection for the steel exposed to such conditions compared to the uncoated 16Mo3 steel. Furthermore, despite the formation of cracks in the coatings, no spallation from the steel surface was observed. Interconnected porosity in the coatings is suspected to provoke interfacial degradation.