The thermal dehydration of copper(II) chelates of O-/N-donor ligands, viz. salicylhydrazide (SH), 5-bromo-salicylhydrazide (5BSH), salicylamide (SAM), nicotinamide (NIA) and gallic acid (GA) has been investigated from the analysis of kinetic data obtained from thermal techniques (TG, DTG, DTA). The statistical analysis of activation energy ( E∗) and of log Z values shows the validity of a linear compensation law. The change in the stereochemistry as a consequence of dehydration has been investigated from X-ray K-absorption spectra. The final residue was identified by far-IR as well as X-ray K-absorption spectra.