AbstractThe utility of mass spectrometry as a technique for the characterisation of polymeric formulations is discussed in general terms. The use of thermal techniques in which sufficient energy is given to the system to liberate volatile components of the formulation and, in some cases, to induce small amounts of polymer degradation, is described. Results obtained using this technique for a variety of polymer systems are discussed and the advantages of using this approach outlined. Recent developments in field desorption‐mass spectrometry for the direct characterisation of modern polymer systems are discussed and some early results presente