In previous work, we have developed a dual physically cross-linked hydrogel composed of poly (acrylamide-co-acrylic acid) (PAM-co-PAA) and polyvinyl alcohol (PVA), named as PVA/CP DN gel, by facile copolymerization and freezing/thawing. The PVA/CP DN gel is featuring both excellent mechanical properties and self-healing ability. Additionally, we have preliminarily found that the comonomer ratio for PVA/CP DN gel have great influence on the self-healing efficiency. In this research article, we will further discuss the mechanical and self-healing properties of the PVA/CP DN gel by varying the comonomer ratio of PAM-co-PAA. The results proved that the structure of DN will be loosen when the number of PAA segments exceed that of PAM. More PAA segments in copolymer make the PVA/CP DN gel have better elongation at break but weak in tensile strength and young’s modulus because of less PVA crystalline domains formed in the gel. The energy dissipation value for the double-network hydrogel decrease with the addition of PAA segments, whereas self-healing efficiency of PVA/CP DN gel increased. Anyway, this work provides more information to further understand the effects of composition on the properties of dual physically cross-linked PVA/CP DN hydrogel.