Direct and headspace gas chromatographic analysis is compared for the determination of lactic, oxalic, succinic, malic and citric acids. For better chromatographic behaviour, prior to GC analysis carboxylic acids were derivatized using BSTFA as a silylation reagent. Three solvents – acetone, diethyl ether and dimethylformamide – were tested as a derivatization medium and DMF was considered as the best. Derivatization conditions were optimized and analytical characteristics of the direct gas chromatographic determination of analytes in solutions were determined. The method was applied for the determination of citric acid in food. For the analytes dissolved in DMF, the headspace gas chromatographic determination was not sensitive enough. Concentrations of the derivates in the headspace were very low, thus the limits of detection were high and the method was not of practical use. On the other hand, headspace gas chromatography can be applied for identifying of carboxylic acids in solid samples.