A simple and highly efficient method for the preparation of formylated amines by reacting amines with formic acid in the presence of metal exchanged tungstophosphoric acid catalyst under solvent free conditions is reported. The catalysts were characterized by X-ray diffraction, FT-infrared, laser Raman, pyridine adsorbed FT-infrared spectroscopies and temperature programmed desorption of ammonia. Fe exchanged tungstophosphoric acid gave high yield compared to other metal exchanged heteropolytungstate catalysts. The efficiency of the catalysts is explained based on their characteristics. The catalyst exhibited consistent activity upon reuse.