Bed materials provide efficient heat transfer and catalytic function in the thermochemical conversion of biomass, but their interactions with the fuel remain incompletely understood. In this study, the effects of bed materials on alkali release and fuel conversion during wood pyrolysis and CO2 gasification are investigated by online alkali detection combined with thermogravimetric analysis. The investigated bed materials include silica, sea sand, alumina and the natural ores olivine, ilmenite and dolomite. Only dolomite has a significant effect on fuel mass loss and alkali release during wood pyrolysis, while all bed materials influence char reactivity and alkali release during gasification. Sea sand, alumina and dolomite enhance the char gasification during the whole or most of the gasification process, which is related to alkali migration from the bed materials. All bed materials affect char reactivity and alkali release when the conversion approaches completion, and small amounts of some bed materials reduce the alkali release by an order of magnitude. The findings can be understood based on the chemical composition of the different materials. Silicon-rich materials reduce the levels of catalytically active alkali by formation of stable alkali silicates, and a similar explanation applies for ilmenite that captures alkali efficiently. Magnesium and calcium in contrast promote alkali release through their influence on alkali silicate chemistry. Analysis of char surfaces using scanning electron microscopy with energy dispersive spectroscopy indicates that low amounts of several elements are transferred from the bed material to the char where they may be directly involved in the char conversion process. The transferred elements are specific for each bed material and relates to their chemical composition. Mechanisms for material exchange between bed material and char are discussed.