3D bioprinting is an acclaimed technology to develop architecturally significant tissue models, however most bioinks require a secondary support structure to create a clinically relevant sized model. In this work, we develop a 3D sacrificial support structure of polyvinyl alcohol (PVA) with decellularized liver extracellular matrix (dECM) bioink with HepG2 cells. The PVA backbone imparts its 3D structure to dECM and dissolves in cell culture media. We evaluated the PVA dissolution using refractometry and microscopic observation. We further tested the crosslinking of dECM with a PEG-based crosslinker using scanning electron microscopy (SEM). Alamar blue assay and gene expression analysis results demonstrated an increase in cell proliferation within the 3D structure.