Native calf thymus double stranded DNA (ct-dsDNA) is successfully immobilized from solution onto carbon substrates by covalent linkages under an optimized deposition potential of 1.8±0.3 V vs.50 mmol/L NaCl-Ag/AgCl.The long chain DNA fabricates a layer of well conductive nano-netting intertexture, which is stable in pH 14 alkaline solution and in boiling water.The ct-dsDNA modified carbon fiber disk electrode shows two to three orders of magnitude enlarged electrode effective surface area and similarly enlarged voltammetric responses to Co(phen)33+ and dopamine.Thermal dissociated single stranded ct-DNA can also lead to similar result.This modified electrode will find wide applications in the fields of DNA-based electrochemical biosensors.