Synthetic scaffolds show great promise for use in tissue engineering due to their ability to mimic some aspects of the extracellular matrix, however, their use has been hindered by the lack of inherent recognition sites that are required for protein and cell interactions. Heparan sulfate (HS), a glycosaminoglycan polysaccharide present in the basement membrane and on the cell surface, binds growth factors and cytokines and enhances the signalling of these ligands by forming complexes with their receptors. This study focuses on the formation of photopolymerised hydrogels derived from methacrylated macromers of poly(vinyl alcohol) (PVA) and heparin, with the aim of imparting the growth factor activation property of heparin to the synthetic scaffolds. It was shown that the methacrylate group attachment on heparin did not result in the fragmentation of heparin molecules, and that the biological activity of the methacrylated heparin was preserved as determined by tests on its anticoagulation properties and ability to signal fibroblast growth factor-2 (FGF-2). The addition of heparin into the PVA hydrogels resulted in an increase in mass swelling ratio from 5.8 for pure PVA to 6.5 and 6.6 for PVA/heparin co-hydrogels of 19/1 and 17.5/2.5 (w/w) compositions, respectively. It is believed that heparin molecules can be added into a synthetic PVA scaffold without adversely affecting the structural and mechanical stability of the PVA scaffold. The tensile moduli of the co-hydrogels remained close to that of PVA hydrogels (61 kPa), even up to 2.5% heparin composition (PVA/hep 17.5/2.5). Finally, the co-hydrogels were found to retain the growth factor signalling activity of heparin at equilibrium.