To develop planar microchemical pCO2 sensing devices with improved electrochemical properties, we combined two advanced technologies. One is a differential sensor arrangement to simplify the microfabrication procedure by employing pH-sensitive gas-permeable membranes, and the other is the use of an enzyme (carbonic anhydrase) to shorten total measurement time by accelerating the rate of CO2 hydration. The adhesion of the polyurethane-matrix gas-permeable membrane is enhanced significantly by incorporating a silanizing reagent (silicon tetrachloride), improving the stability and extending sensor lifetime. The proposed differential pCO2 microelectrodes exhibited significantly improved performance in their preconditioning period, response and recovery times, stability, response slope, and lifetime.