Impure formic acid cannot be completely removed from formic acid-water-impurity mixtures by distillation because of the presence of the maximum azeotrope between formic acid and water. Formic acid can be readily removed from mixtures containing it, water and impurities of the ether, ester, ketone or diketone type by using extractive distillation in which the extractive agent is a higher boiling oxygenated, nitrogenous or sulfur containing organic compound or a mixture of these. Examples of effective agents are adiponitrile; sulfolane and salicyclic acid; dimethylformamide, N,N-dimethylacetamide and ethylene glycol ethyl ether acetate.