Single square voltage pulses were used to enhance by 7 and 9 orders of magnitude the rate of covalent immobilization and hybridization, respectively, of single stranded DNA probes on a chemically functionalized thin film surface (silicon dioxide) using 2 mm size electrodes. These electrodes were scaled down to 20 μm. Photolithography was used to define the electrode voltage line, ground line, and functionalized thin-film area on a plastic substrate (polyimide). At all electrode dimensions, electric field-assisted DNA immobilization and hybridization can be achieved in the microsecond time scale, far faster than the 2 hr or 16 hr needed for immobilization and hybridization, respectively, without the electric field. Pulse conditions optimized with the large-size electrodes (2 mm) were used in the microelectrodes.