The potential slag formation behavior during pressurized entrained-flow gasification (PEFG) of woody biomass has been studied from a thermodynamic perspective with respect to compositional, temperature, and pressure variations. An ash transformation scheme was proposed on the basis of the melt formation potential that arises when gaseous K species are present with Si and Ca. Databases and models in FactSage 6.4 were used to carry out thermochemical equilibrium calculations within ChemSheet. It was found that increasing pressure and increasing Si content expanded the range of operating conditions that are conducive of melt formation, while increasing temperature and increasing Ca content diminished the range. The results from the calculations compared qualitatively well to experimental results and provide further information needed in the development of PEFG reactors for woody biomass.