In this work, the network structure and chain mobility of dried polyvinyl chloride/dioxane (PVC/DOA) gels prepared by the freeze-drying method are studied by SEM, FTIR, WAXD, EDTA and pulsed NMR analyses. The results of FTi.r. and WAXD show no remarkable change in the crystallinity of either dried or wet PVC gels; however, the elasticity of wet gels and the gelation time of semi-dilute solutions exhibit remarkable changes with increasing concentration, C and molecular weight, M-W of the polymer. From SEM results, the dried gel morphology consists of a fibril-like structure and the mesh size of the gel network decreases, resulting in the glass transition temperature (T-g) shifting to higher temperatures with increasing M-W and C. The results of pulsed NMR (CPMG method) for wet gels show that spin-spin relaxation time, T-2(s) and T-1(l) respectively, related to the immobile and mobile components decrease, and the fractional amount of the immobile component,f(s) increases, while that of the mobile component, f(l) decreases with increasing M-W and C. On the other hand, similar results are also found in freeze-dried gels from the pulsed NMR experiment (FID method). These facts in both wet and dried gels are considered to be due to the reduction of chain mobility related to the increase in the aggregation of polymer chains or the number of junction points in the gel network. The change in elasticity of PVC/DOA gels must be mainly related to the chain mobility of the network structure but not to the crystallinity of gels.