A method to integrate a carbon microelectrode with a microfabricated palladium decoupler for use in microchip capillary electrophoresis (CE) is detailed. As opposed to previous studies with decouplers for microchip CE, the working electrode material, which is made by micromolding of a carbon ink, is different from the decoupling electrode material (palladium). The manner in which the working electrode is made does not add additional etching or lithographic steps to the fabrication of the glass electrode plate. The hybrid poly(dimethylsiloxane)/glass device was characterized with fluorescence microscopy and by monitoring the CE-based separation of dopamine. Hydrodynamic voltammograms exhibited diffusion-limited currents occurring at potentials above +1.0 V. It was also shown that the half-wave potential does not shift as the separation potential is changed, as is the case in nondecoupled systems. Gated injections of doparnine in a 25 mm boric acid buffer (pH 9.2) showed a linear response from 200 to 5 gm (r(2) = 0.9992), with a sensitivity of 5.47 pA/mum and an estimated limit of detection of 2.3 mum (0.621 fmol, S/N = 3). This is the first report of coupling a carbon electrode with a decoupler in microchip CE.