PVC forms gels in a number of solvents. Measurements of gel melting temperature as a function of molecular weight and concentration indicate that the cross-links result from H bonding between two segments. Crystallization in the gels in the form of two types of crystals is independent of the gel network formation, growing after the gel forms. The gel-forming ability and gel hardness are functions of the polymer-solvent interaction and the H-bonding ability of the solvent. Replicas of freeze-fracture-etched surfaces of the gels suggest aggregation of the PVC molecules in the form of a fibrous network structure.