Several methods for the preparation of polyvinyl alcohol (PVA) hydrogel are being reported in the literature. In this communication a new, simple, and mild complexation reaction using phenyl boronic acid, leading to a highly elastic PVA hydrogel, is addressed. It is found that the inherent crystalline property of the semicrystalline PVA is retained by the complexation reaction, which is confined to the amorphous region. An enhanced mechanical property, particularly in the wet condition, is observed after the modification resulting from the intact crystallinity. Also, the inherent nontoxic characteristic property of PVA is unaffected upon this complexation reaction.