Electrospun fibers with contrasting cell adhesion properties provided non-woven substrates with enhanced in vitro acceptance and controllable cell interactions. Poly(ethylene glycol)-block-poly(epsilon-caprolactone) (PEG-b-PCL) block copolymers with varying segment lengths were synthesized in two steps and characterized by NMR and GPC. A cell adhesive peptide sequence, GRGDS, was covalently coupled to the PEG segment of the copolymer in an additional step. The suitability of polymers with molecular weights ranging from 10 to 30 kDa for electrospinning and the influences of molecular weight, solvent, and concentration on the resulting morphologies were investigated. Generally, electrospun fibers were obtained by electrospinning polymers with molecular weight larger than 25 kDa and concentrations of 10 wt%. Methanol/chloroform (25/75, v/v) mixtures proved to be good solvent systems for electrospinning the PEG-b-PCL and resulted in hydrophilic, non-woven fiber meshes (contact angle 30 degrees ). The mesh without cell adhesive GRGDS ligands showed no attachment of human dermal fibroblasts after 24 h cell culture demonstrating that the particular combination of the material and electrospinnig conditions yielded protein and cell repellent properties. The GRGDS immobilized mesh showed excellent cellular attachment with fibroblasts viable after 24 h with spread morphology. Electrospun nanofibers based on block copolymers have been produced which are capable of specifically targeting cell receptor binding and are a promising material for tissue engineering and controlling cell material interactions.