Global warming and air pollution are two issues of greatest concerns to human life in recent years. Environmental concerns and econimal/political independency of fossil fuels have been the driving force of developing interest in renewable resources of energy for many countries. Different type of waste-derived fuels such as biomass, municipal solid waste and industrial waste are interesting energy resources for energy producing companies. There are mainly two main paths when it comes to waste-to-energy industry, which are thermal treatment of waste, as well as biochemical treatment. Thermal treatment of waste to produce energy could benefit both for hygienic consideration of waste management and avoiding waste landfill.Heat and power generation through combustion of waste or biomass has several environmental, and economical advantageous over utilization of fossil fuels. Thermal conversion of waste and biomass fuels, however, has some challenges mainly due to their chemical composition and high alkali metals (potassium and sodium) content. Combustion of these fuels usually can result in some operational challenges such as deposition, fouling, bed agglomeration and corrosion in different part of the boiler. The less reactive and non-combustible part of the fuel known as ash-forming matter has a major role in these operational challenges. Ash related problems in waste-to-energy boilers lead to lower efficiency, high maintenance costs and equipment failure. Therefore, investigating the chemical composition of fuel and ash-forming matter is essential prior to thermal conversion of waste-derived fuels. High-temperature corrosion due to formation of corrosive alkali chloride compounds during combustion is one of the main ash-related concerns in boilers.This study investigated high-temperature corrosion in circulating fluidized-bed (CFB) combustion of solid waste. Flue gas composition of solid waste combustion in the CFB boiler was analysed in two cases: combustion of the reference fuel, and combustion of the “same” fuel with a sulphur containing additive (ammonium sulphate), to decrease the corrosive alkali chlorides in the flue gas. Chemical fractionation was carried out for fuel samples to determine the reactive and less-reactive fraction of ash-forming matter. A thermodynamic equilibrium model was developed using Factsage thermochemical software, to predict the chemical composition of the flue-gas with a special focus on corrosive alkali chlorides. The modelling results were evaluated using In-situ Alkali Chloride Monitoring (IACM) results obtained during the full-scale combustion measurements.