PVA hydrogels with high strength and toughness are fabricated by dual physical and chemical cross-linking. The best comprehensive mechanical properties can be achieved by reaction at room temperature followed with freeze-thaw and annealing treatment. Besides, the mechanical properties of PVA hydrogel increased first and then decreased with the increase of molecular weight or mass fraction. By changing the reaction solvent, the mechanical properties of PVA hydrogel could also be effectively adjusted. Therefore, the influences of various factors on the mechanical properties of PVA hydrogel can be obtained.