The biological modification of biomaterials surface was an important means for surface endothelialization. In this work, an extracellular matrix-like (ECM-like) surface modification was developed for inducing endothelialization on titanium cardiovascular implant surface. To solve the problem of antibody denaturing caused in the randomly immobilizing, cluster of differentiation 34 (CD34) antibody was directly immobilized on titanium surface using a layer-by-layer self-assembly (LBL) technique. The biological behaviors of the endothelial progenitor cells (EPCs) on modified titanium surface were investigated by in vitro cell culture experiment. The results showed that the avidin, biotinylated protein A and the CD34 antibody were successfully assembled onto the NaOH etched titanium surface. The results of cells experiment suggested that the CD34 antibody immobilized surfaces promoted EPCs attachment and capture in vitro. It was believed that the response of adhesion, proliferation, differentiation of EPCs to titanium surface was regulated by modifying the surface chemistry which controlled the cell-biomaterial interactions. This work provided a surface biomodification means to increase the biocompatibility of titanium-based vascular implant surfaces.