The response of human endothelial cells (ECs) to poly(ε-caprolactone) (PCL) and eight different PCL modifications was examined in vitro. In CLSM, cell proliferation and viability testing, ECs responded best to plasma chemical activation of PCL. When ECs were additionally stimulated by VEGF, their maximum response was again seen on plasma activated PCL. Polymer precoating with matrix proteins was found to be beneficial for EC adhesion. A qPCR study of eNOS, IL-8, ICAM-1, PECAM-1 and VCAM-1 transcripts after VEGF stimulation of ECs on four modified and coated PCL surfaces was also performed.