We fabricated an electrochemical detector (ECD) to catalyze redox reaction efficiently by electrodepositing Prussian blue (PB) on the indium tin oxide (ITO) electrode. Capillary electrophoresis (CE) and amperometric method were used. We investigated the PB surface properties by topography from atomic force microscopy (AFM). Also PB film thickness calibration with respect to deposition time and voltage was used to get better PB surFace. The PB thin film of dense and smooth surface could catalyze redox reaction efficiently. Comparing with CE-ECD microchip using bare-lTO electrode, proposed CE-ECD microchip using PB deposited electrode has shown better sensitivity by determining the detected peak current from the electropherograms while the concentration of tested analyzes was maintained the same. It is verified that detection limit can be lowered for 0.01 mM of dopamine and catechol respectively.