AbstractRapid volatile matter evolution from high‐volatile fuels such as wastes and biomass is one of problems associated with fluidized bed incinerators and gasifiers. When volatile matter evolves rapidly in the vicinity of the fuel feed point, the mixing of volatile matter with reactant gas is poor, and therefore, unreacted volatile matter is expected to be released from the reactor. In the present work, reduction of the volatile matter evolution rate was attempted by employing porous solids as bed materials instead of nonporous sand. The effect of bed material on the onset of devolatilization was measured by use of a bench‐scale bubbling fluidized bed reactor. Volatile matter capture by the porous solids (capacitance effect) and the heat transfer rate within the bed, both of which affect volatile matter evolution rate, were also measured. Four types of porous solids, both with and without capacitance effect, were employed as the bed material. By employing porous solids without capacitance effect, the contributions of reduced heat transfer rate and capacitance effect to the delay of volatile matter evolution can be evaluated separately. For porous bed materials with a moderate capacitance effect (volatile matter capture of up to 20 %), the delay of the onset of devolatilization, which was measured by detecting the flame combustion of the volatile matter, was explained by the lower heat transfer between the fuel and bed. However, for a porous particle with high capacitance effect (volatile matter capture of 30 %), the capacitance effect also affected the delay of the onset of the flame combustion.