Diethanoldithiocarbamate complexes with Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) were prepared and characterised by elemental analysis, infrared spectroscopy and flame atomic absorption spectroscopy. Their thermal decomposition was investigated by TG/DTG and DSC techniques under dynamic air and nitrogen atmospheres. These studies showed that the smaller the metallic ionic radius the higher was their thermal stability and that the bidentate complex decomposed in a direct way, with no evidence of thyocyanate intermediates.