A sensitive electrochemiluminescent detection scheme by solid-phase extraction at Ru(bpy)3(2+)-modified ceramic carbon electrodes (CCEs) was developed. The as-prepared Ru(bpy)3(2+)-modified CCEs show much better long-term stability than other Nafion-based Ru(bpy)3(2+)-modified electrodes and enjoy the inherent advantages of CCEs. The log-log calibration plot for dioxopromethazine is linear from 1.0 x 10(-9) to 1.0 x 10(-4) mol L(-1) using the new detection scheme. The detection limit is 6.6 x 10(-10) mol L(-1) at a signal-to-noise ratio of 3. The new scheme improves the sensitivity by approximately 3 orders of magnitude, which is the most sensitive Ru(bpy)3(2+) ECL method. The scheme allows the detection of dioxopromethazine in a urine sample within 3 min. Since Ru(bpy)3(2+) ECL is a powerful technique for determination of numerous amine-containing substances, the new detection scheme holds great promise in measurement of free concentrations, investigation of protein-drug interactions and DNA-drug interactions, pharmaceutical analysis, and so on.