Abstract Chars produced from lignites typically have much higher reactivities to gasification than those produced from bituminous coals. This has been attributed previously to the presence of carboxylate salts of inorganic constituents on the lignites. Upon charring of the lignites, the carboxylate salts decompose leaving behind well dispersed inorganic constituents which act as catalysts for gasification. In this study, a raw lignite has been treated with HCl and HF to demineralize it and to increase its carboxyl content prior to exchanging selected cations with the hydrogen on the carboxyl groups. Up to 2.14 mmol of calcium per g of coal could be added using this procedure. Addition of varying amounts of calcium to the lignite resulted in the production of chars containing calcium contents ranging from 1.1 to 12.9 wt %. Such addition resulted in a rectilinear increase in reactivity of the char to steam with increasing amount of calcium added. Maximum reactivity attained was over ten times the reactivity found for the char produced from the raw lignite. At comparable molar loadings of metal cations onto the acid-treated lignite, the chars subsequently produced had reactivities in steam in the order: K > Na ≈ Ca > Fe > Mg. Char reactivity could also be enhanced by the addition of cations to nitric acid-treated char which had been produced, in turn, from demineralized lignite.