An agarose gel was used as an electrochemical cell to graft vinylic polymer layers on conductive surfaces by electro-initiated radical electrografting of various water-soluble and hydrophobic vinylic monomers in the presence of diazonium ions. The process was followed by in situ electrochemical measurements and the resulting grafted layer was characterized by infrared (IRRAS) and photoelectron (XPS) spectroscopy.