The coordination adducts of MnCl2, FeCl3, CoCl2, NiCl2 and CuCl2 with DMF were isolated and characterized by elemental analysis, magnetic moments, UV-VIS spectroscopy, IR spectroscopy and thermal analysis techniques. The shift of the CO stretching vibration to low frequency indicated that DMF is bonded through oxygen to the metals. On the basis of spectral and elemental analysis data, the complexes have dimeric and trimeric structures achieved by the chlorine bridges. The complexes do not have melting points and undergo decomposition after dehydration. The decomposition of DMF in the complexes occurs in several stages and the last stages of decomposition always corresponds to decomposition or sublimation of the respective metal chlorides to produce the respective metal.