Clinical drug development suffers largely due to the inability of in vitro 2D culture studies to precisely predict the physiological effect of drug toxicity. Three dimensional (3D) cell culture can provide solution to this problem since behaviour of cells in 3D culture closely resemble their behaviour in physiological conditions. This study investigates the application of a synthetic extracellular matrix (ECM) mimic as a three dimensional environment for culturing liver cells expressing considerable functionality. The synthetic hydrogel, polyethylene glycol diacrylate (PEGDA) was used in this study as a support environment for the cells. PEGDA of two different molecular weights (4000 Da and 400 Da) and their composites at different weight percentage ratio were investigated for their swelling properties, pore size and cell viability. Since liver architecture is paramount for its effective functioning, projection based stereolithographic printing is used in this study for printing complex 3D structures. Based on the results, 30 wt % PEGDA MW 4000 Da was chosen to assess liver functionality as they were biocompatible and also showed promise to be optimized for printing complex structures. Liver cell functionality was assessed using Enzyme linked immunosorbent assay (ELISA) for albumin secretion and Cytochrome P450 enzyme assay. While studying heterotypic cell-cell interactions by co-culturing fibroblasts with liver cells, it was observed that fibroblasts indeed enhanced the functionality of the liver cells encapsulated in the hydrogel. Based on the results of this investigation, it can be inferred that PEGDA can serve as a 3D printable, bio-functional liver cell scaffold.