In this work, CE separation with end-column Ru(bpy)(3)(2+) ECL detection for the quantitative determination of pentoxyverine was firstly performed. The experimental conditions, such as the applied potential, injection voltage, injection time, and the pH of separation buffer, were discussed in detail. Gold nanoparticles were found to enhance the ECL intensity at an appropriate volume ratio of nanogold with Ru(bpy)(3)(2+) but without changing their nanoproperties proved by transmission electron microscopy (TEM) and UV-vis spectra. The detection limits with or without nanogold were 6 nM and 0.6 mu M, respectively. Successful separation of pentoxyverine, chlorpheniramine, and lidocaine was achieved. This method was also applied to monitor drug binding with HSA, and the binding constant for pentoxyverine was estimated as 1.8 x 10(3)/M.