Interactions between vascular endothelial cells (ECs) and biomaterials are important for engineered tissue substitute. The modification of biomaterial surfaces are designed to modulate EC adhesion and responses in order to improve implantation success rate. Specifically, it has now been well established that increased vascular tissue regeneration can be achieved on almost any surface by employing novel nanofabricated surface features. To enhance EC adhesion and growth, material surfaces have been modified with physicochemical and mechanical properties, such as bioactive molecules from the matrix, peptides, and/or growth factors to control EC behavior. The advances in nanotechnology can bring additional functionality to vascular tissue engineering, optimize internal vascular graft surface, help to direct the differentiation of stem cells into the vascular cell phenotype, and, most importantly, also provide a biomaterials-based cellularization process. Nanomaterials could promote in situ endothelialization by mobilizing endothelial progenitor cells (EPCs) from the bone marrow, by encouraging cell-specific adhesion to the vascular graft, and, once attached, by controlling the proliferation and differentiation of these cells. Interaction between different cell types and extracellular matrix continue to be a principal source of inspiration for material biological function and, therefore, the understanding of the molecular mechanism trigger by the interaction is discussed.