Abstract Doping a 1wt.% Pd/C catalyst with alkali metal carbonates has a very significant promotional effect on its activity in hydrogen production from the decomposition of formic acid vapour (2vol.%, 1bar), potassium and caesium carbonates giving the largest effects. The K carbonate species present on the fresh catalysts react with formic acid to form formate ions, these being dissolved in a formic acid/water solution condensed in the pores of the support. The steady-state activities of the samples containing formate ions were 1–2 orders of magnitude greater than those of the unpromoted Pd/C and CO content was lower than 30ppm. The activation energies for the reaction increased with doping from 66 to 88–99kJmol−1, relatively independent of the cation of the dopant. Similar but lesser effects were found with unsupported Pd nanocrystals doped with K carbonate. The rate-determining step for the promoted samples appears to be the decomposition of formate ions on the Pd surface.