Biomass has great potential to become an economic source of renewable energy; however, its high chlorine and alkali metal content may cause series problems (e.g. slagging and corrosion) thus limiting its utilization. This paper reviews the release of potassium during biomass thermal conversion. Organic potassium is released first when the temperature is relatively low, starting at about 473 K and slowing down at about 773 K; the release of inorganic potassium occurs with the increase of processing temperature. The potassium vapors are mainly in the form of KCl, KOH and K2SO4. In addition to the temperature, the properties of biomass, fuel-air ratio, pressure and heating rate also significantly influence the release rate of alkali metals. Future studies are required to develop accurate kinetic models of potassium release to address the ash related challenges when firing and co-firing biomass with high inherent alkali content.