Electron beam, thermal free radical, and cationic complexation mechanisms have been employed to investigate crosslinking in selected polyphosphazenes. In polyphosphazenes functionalized with o-allylphenol to facilitate free radical crosslinking, maximum crosslink density was achieved after 10 min at 130 degrees C utilizing benzoyl peroxide as an initiator. Electron beam radiation was found to give an increased crosslink density with increased dose. The dose-crosslink density relationship observed for a aryloxyphosphazene terpolymer PPXP also was seen in poly[bis(2,2＇-(methoxyethoxy)ethoxy)phosphazene] (MEEP). However, with two lots of a fluoroalkoxyphosphazene an initial crosslink density was achieved at a lower electron beam exposure with no additional crosslink density observed with increasing dose. These measurements are observations of net crosslinking, which is the result of crosslinking processes balanced by chain scission processes. DSC revealed that neither thermal- nor electron beam-initiated crosslinking cause any significant change in the T-g, of the polymer. Metal ion complexation with MEEP consistently gave T-g values that were higher than MEEP. The T-g values measured for both MEEP and the lithium-complexed MEEP were unaffected by electron beam irradiation. These data suggest the location of lithium complexation may be at the nitrogen lone electron pair on the backbone, representing a new mechanism of lithium complexation in phosphazenes. (C) 2000 John Wiley & Sons, Inc.