The development trends in the energy sector clearly indicate an increase in the share of biomass and alternative fuels fed for combustion in power boilers, which results in the imposition of many unfavourable factors and a demanding working environment. During the operation of the energy system, this means a sharp increase in corrosion of the gas-tight pipe walls and coils by the destructive action of chlorine and sulphur. Implementing advanced surface protection in addition to the selection of materials of better quality and resistance to difficult working conditions would significantly reduce their wear by high temperature corrosion. Thermally sprayed coatings offer a great opportunity to protect machine components and energy systems against corrosion, erosion, impact load and abrasive wear. This article presents the test results of high-temperature corrosion resistance of coatings made with Ni-Cr-B-Si and Ni-B-Si alloy powders on a boiler steel substrate. Samples with sprayed coatings were exposed to an atmosphere with a composition of N2 + 9% O2 + 0.08% SO2 + 0.15% HCl at 800 °C for 250, 500, 750 and 1000 h. Tests results of coatings made of Ni-Cr-B-Si alloys subjected to the influence of a corrosive environment showed the formation of a layer of scale on the surface, composed mainly of Cr2O3 oxide, which was a passive layer, reducing the rate of corrosion. Coatings sprayed with Ni-B-Si alloys showed significantly lower corrosion resistance. It was found that the developed technology of subsonic flame spraying with powders of the Ni-Cr-B-Si type allows the production of coatings compliant with the requirements of the energy industry, which allows their use as anti-corrosion protection on boiler elements intended for waste disposal and biomass combustion.