The integration of biomaterials with living cells and stimuli-responsive materials can be employed to create bioinks capable of generating 3D in vitro models that better recapitulate native tissues. A cellularized, multilayered cylindrical model is introduced that combines such hybrid multifunctional materials to mimic the tunica adventitia arterial wall, and an extracellular matrix (ECM)-based bioink for the tunica media artery layer. The stimuli-responsive hybrid ink integrates inorganic (plasmonic nanoparticles) and organic (polymers) components, providing structural support and introducing diverse functionalities to the system. The cell-laden bioink consists of human vascular smooth muscle cells within a hydrogel based on porcine artery-derived decellularized ECM that fosters optimal cell growth and proliferation. An embedding bioprinting technique is employed for the fabrication of the multimaterial model consisting of functional concentric cylinders. The dimensions of the 3D model and the bioprinting parameters are fine-tuned to ensure effective crosslinking of the multiple concentric layers resulting in the creation of self-supporting constructs. The effectiveness of the hybrid bioink composition and bioprinting parameters in supporting cell viability and proliferation within the multilayered construct is demonstrated, expanding the possibilities of employing novel multi-component materials for the fabrication of 3D vasculature models resembling the structure of native blood vessels.