In this study, poly(vinyl alcohol)/chitosan (PVA/CS) scaffolds were fabricated by freeze-drying method and the characterisations of obtained scaffolds were carried out to analyse the suitability of the product for biomedical applications such as tissue engineering. The effect of initial PVA concentrations and their hydrolysis degrees, the addition of different molecular weights (MWs) of CS along with the blending ratio of PVA/CS were studied. Fourier transmission infrared (FTIR) spectroscopy showed the presence of chemical bonds in PVA and PAV/CS scaffolds and the energy dispersive X-ray (EDX) spectroscopy confirmed the existence of the chemical element nitrogen in PVA/CS scaffolds. The stability of scaffolds under physiological conditions was studied by swelling and degradation tests, which demonstrated the effect of initial PVA concentration and CS addition on the water resistance of scaffolds. Scanning Electron Microscopy (SEM) images showed highly porous structures which became more uniform in pore size with the addition of CS. The mechanical properties of dry and hydrated scaffolds were also investigated by an unconfined compression test and the compressive modulus and maximum stress at 20% strain were calculated through stress–strain curves. The in-depth characterisation of scaffolds showed that the initial concentration and blending ratio of PVA/CS can be adjusted to tailor the desired properties of scaffolds for different biomedical applications.