For the reconstruction of functional tissue, biodegradable scaffolds providing specific surface functionality and a three-dimensional structure matching that of the damaged tissue are needed. Fibers capable of controlling cell-fiber interaction were produced by electrospinning of PDLLA-block-PEG with thiol-reactive end groups from a solvent mixture. The hydrophilic fibers uniquely combine minimized non-specific protein adsorption and well-defined surface reactivity allowing controlled immobilization of peptides and proteins. Human dermal fibroblasts show adherence and proliferation on the surface of RGDC-functionalized electrospun PDLLA-block-PEG fibers.