The crosslinking of poly(vinyl chloride) (PVC) modified with 4-mercaptobenzyl alcohol is studied as a function of the number of hydroxyl groups present in the polymer and the amount of crosslinking agent added. Comparison of crosslinking reaction of a hydroxylated PVC polymer synthesized in our laboratory and a commercial system shows a higher reaction rate and degree of conversion for the former. Swelling experiments of partially crosslinked polymers reveal the existence of two kinds of interpenetrated networks, chemical and physical. The appearance of the physical network is due to hydrogen bonding interactions between the remaining hydroxyl groups in the polymer chains after crosslinking. Thermogravimetric analysis and traction tests show good thermal stability of the networks obtained, and a significant improvement in the mechanical properties with respect to linear PVC. M-c values obtained from swelling experiments, mechanical tests and dynamomechanical tests are in agreement with the theoretical values,