This paper presents an overview of the synthetic procedures used for the preparation of phosphazene compounds. The main reactions used in this field, i.e. ring-opening polymerizations, polycondensations and free-radical processes, have been critically reviewed and the possibility of controlling these reactions by using catalysts or inhibitors evaluated. Both low-molecular-weight linear and cyclic phosphazene oligomers and high-molecular-weight phosphazene polymers have been considered. (C) 1998 Elsevier Science Ltd.