Chlorine dioxide is potentially a powerful oxidant with environmentally compatible application in several strategic areas relating to pollution control typically for water disinfection, and its sustained production is a key factor for its successful application. Although increased attention has been paid for on-line chlorine dioxide generation by several chemical and electrochemical methods, the details are mostly confined as patents. We studied in this work the electrochemical generation of chlorine dioxide from an un-buffered solution of sodium chlorite and sodium chloride mixture in an un-divided electrochemical cell under constant current mode, with a view to optimize various process parameters, which have a direct bearing on the chlorine dioxide formation efficiency under laboratory conditions. The effect of feed flow rate (10-150 ml min(-1)), feed solution pH (2.3-5.0), concentration of sodium chloride (0-169.4mM), concentration of sodium chlorite (0-7.7 mM), and the applied current (100-1200 mA) on the formation of dissolved ClO(2) gas in solution and the pH of the product-containing solution was investigated by performing single pass experiments, with no circulation, in a cell set-up with Ti/IrO(2) anode and Ti/Pt cathode. The current efficiency and the power consumption were calculated for the optimized conditions.