To improve the endothelization of 3D matrices produced by electrospinning we propose adding cyclo(RGDfC) peptide conjugated to human serum albumin (HSA) (HSA-c(RGDfC)) to the electrospinning solution. HSA-c(RGDfC) has been prepared using a bifunctional linker with N-hydroxysuccinimide and maleimide groups, and the product has been confirmed by 1Н NMR spectroscopy. Electrospun matrices have been fabricated from the solutions of 3% polyurethane Tecoflex EG-80A with 10% HSA and 0.01–1.3% HSA–c(RGDfC) (relative to Tec) in 1,1,1,3,3,3-hexafluoro-2-propanol. The presence of HSA and the cyclo(RGDfC) peptide on the surface of electrospun matrices has been confirmed by FTIR spectroscopy. The structure of matrices has been examined by scanning electron microscopy. The ability of the matrices to facilitate the adhesion of primary human umbilical vein endotheliocytes (HUVECs) has been studied. The presence of HSA–c(RGDfC) conjugate in the matrices enhanced cellular adhesion in a dose dependent manner with a maximum effect at 1% HSA-c(RGDfC).