Thermal degradation characteristics of some poly[poly(ethylene glycol)] phosphates (PPEGP) based on ethylene glycol (PEGP), an equimolar mixture of ethylene glycol and trigol (PETP), digol (PDGP), and trigol (PTGP) have been studied by combined differential thermal and thermogravimetric analyses (DTA/TGA). It has been shown that, in spite of their structural similarities, the PPEGPs do not conform to any generalized degradation pattern. Local strains in the crosslinked network and the possible intranetwork topographic interferences due to crossovers, entanglements, and varying lengths of polyoxyethylene link units are believed to play a pivotal role in the thermal degradation of individual PPEGPs.