Nanofibrous scaffold of carbon nanotubes/polyurethane composite (MWNT/PU) with aligned topography was fabricated by electrospinning for endothelium cells growth. The diameter of the generated fiber was around 300 nm-500 nm. Experimental results indicated that the nanofibrous scaffold of MWNT/PU exhibited promotional influence on the cell proliferation. It was also observed that the scaffold possessed an advantage of supporting ECs migrating and aggregating along the axis of the aligned nanofibers, which is one of the important functions in the process of endothelium regeneration. It was also demonstrated that the endothelial cells growing on the scaffold expressed non-thrombogenic phenotype with low tissue factor released. These results indicated the favorable interactions between ECs and the nanofibrous scaffold of MWNT/PU, implying that the aligned nanofibrous scaffold has a promising potential for vascular engineering.