To reduce the use of fossil fuels and increase self-sufficiency in energy, nowadays, there is an increasing interest to produce energy mainly from renewable resources. Solid biomass is one of the most important renewable energy sources for meeting this target. However, fouling, slagging, and corrosion threaten long-term operation availability and costs of biomass power plants. Slags accumulated on the surfaces of superheaters, which decrease thermal efficiency, often constitute a considerable percentage of complex inorganic phases. However, thermodynamic properties of the complex inorganic phases and their combined effect, which will help to deal with the slag related problems during high-temperature biomass combustion processes, are not well known. In the present paper, thermodynamic properties of K-, Ca-, and Na-based inorganic phases and their mixtures under different gas conditions are both critically reviewed and experimentally studied. The obtained results are presented and discussed.