It is well known that preparation method of hydrogels has a significant effect on their properties. In this paper, freeze-thawing and anneal-swelling were applied to prepare poly(vinyl alcohol)/polyacrylamide (PVA/PAM) double-network hydrogels with covalently and physically cross-linked networks. The properties of these hydrogels were investigated and compared to control hydrogels. Results indicated that hydrogels fabricated by freeze-thawing show larger pores size and higher swelling capacity than those made by anneal-swelling and control hydrogels. Hydrogels prepared by anneal-swelling exhibit higher mechanical strength, energy dissipation, fracture energy, gel fraction and crystallinity than those made by freeze-thawing and control hydrogels. Physical cross-linking plays a key role in formation of physical-chemical double-network. The toughening mechanism of double-network hydrogel is related to their chain-fracture behavior and elasticity. The results also indicated that appropriate methods can endow hydrogels with specific microstructures and properties which would broaden current hydrogels research and applications in biomedical fields.