A poly(vinyl alcohol) (PVA) hydrogel composite scaffold containing N, O-carboxymethylated chitosan (NOCC) was tested to assess its potential as a scaffold for cartilage tissue engineering in a weight-bearing environment. The mechanical properties under unconfined compression for different hydration periods were investigated. The effect of supplementing PVA with NOCC (20 wt.% PVA:5 vol.% NOCC) produced a porosity of 43.3% and this was compared against a non-porous PVA hydrogel (20 g PVA: 100 ml of water, control). Under non-hydrated conditions, the porous PVA–NOCC hydrogel behaved in a similar way to the control non-porous PVA hydrogel, with similar non-linear stress–strain response under unconfined compression (0–30% strain). After 7 days’ hydration, the porous hydrogel demonstrated a reduced stiffness (0.002 kPa, at 25% strain), resulting in a more linear stiffness relationship over a range of 0–30% strain. Poisson’s ratio for the hydrated non-porous and porous hydrogels ranged between 0.73 and 1.18, and 0.76 and 1.33, respectively, suggesting a greater fluid flow when loaded. The stress relaxation function for the porous hydrogel was affected by the hydration period (from 0 to 600 s); however the percentage stress relaxation regained by about 95%, after 1200 s for all hydration periods assessed. No significant differences were found between the different hydration periods between the porous hydrogels and control. The calculated aggregate modulus, H A, for the porous hydrogel reduced drastically from 10.99 kPa in its non-hydrated state to about 0.001 kPa after 7 days’ hydration, with the calculated shear modulus reducing from 30.92 to 0.14 kPa, respectively. The porous PVA–NOCC hydrogel conformed to a biphasic, viscoelastic model, which has the desired properties required for any scaffold in cartilage tissue engineering.