This article presents a systematic evaluation of coatings for advanced fossil fuel plants and addresses fireside corrosion in coal/biomass-derived flue gases. A selection of four candidate coatings: alloy 625, NiCr, FeCrAl and NiCrAlY were deposited onto superheaters/reheaters alloy (T91) using high-velocity oxy-fuel (HVOF) and plasma spraying. A series of laboratory-based fireside corrosion exposures were carried out on these coated samples in furnaces under controlled atmosphere for 1000 h at 650 C. The tests were carried out using the “deposit-recoat” test method to simulate the environment that was anticipated from air-firing 20 wt.% cereal co-product mixed with a UK coal. The exposures were carried out using a deposit containing Na2SO4, K2SO4, and Fe 2O3 to produce alkali-iron tri-sulfates, which had been identified as the principal cause of fireside corrosion on superheaters/ reheaters in pulverized coal-fired power plants. The exposed samples were examined in an ESEM with EDX analysis to characterize the damage. Pre- and post-exposure dimensional metrologies were used to quantify the metal damage in terms of metal loss distributions. The thermally sprayed coatings suffered significant corrosion attack from a combination of aggressive combustion gases and deposit mixtures. In this study, all the four plasma-sprayed coatings studied performed better than the HVOF-sprayed coatings because of a lower level of porosity. NiCr was found to be the best performing coating material with a median metal loss of ∼87 μm (HVOF sprayed) and ∼13 μm (plasma sprayed). In general, the median metal damage for coatings had the following ranking (in the descending order: most to the least damage): NiCrAlY > alloy 625 > FeCrAl > NiCr.