In the present work, a series of graphene oxide (GO)/hydroxyapatite (HA)/poly(vinyl alcohol)(PVA) dual cross-linked composite hydrogels were synthesized by applying the combinatorial methods of chemical crosslinking and cyclic freezing-thawing, and varying the mass ra-tios of GO to PVA, HA to PVA and the number of times of cyclic freezing-thawing. Firstly, PVA chains covalently crosslinked at a rather low concentration (considering the bio-safety) of glutaraldehyde for the chemical-crosslinking of the first network. Then, during the cyclic freezing-thawing process, the PVA crystalline domains served as cross-linking knots and the hydrogen-bonding were formed for the secondary physical-crosslinking network. The resultant hydrogels were defined as the GO/HA/PVA dual cross-linked hydrogels. The structure of the GO/HA/PVA nanocomposite hydrogels was characterized by the high-resolution scanning electron microscope and X-ray diffraction. The tensile mechanical properties were further investigated for the dual cross-linked hydrogels differing in mass ratios of GO to PVA (0%-2.6%) and HA to PVA (0.22-1.10), and number of times of cyclic freezing-thawing (0, 3, 7). When the mass ratio of GO/PVA reached to 1.9%, HA/PVA reached to 0.66 and with 7 times cyclic freezing-thawing, the GO/HA/PVA dual cross-linked hydrogel achieved the maximum tensile strength and elongation at break of up to 695 kPa and 286%, and the Young's modulus was 78 kPa. We further investigated the water content and swelling behaviors of dual cross-linked hydrogels with various number of times of cyclic freezing-thawing (0, 3, 7). The results revealed that the water content was about 79.3%-81.7%, and the equilibrium swelling ratio was about 50.1%-72%. The hydrogel was expected to serve as cartilage substitution materials in clinical medicine field. © 2019, Materials Review Magazine. All right reserved.