Over the last 10 to 15 years capillary electrophoresis (CE) has become an extensively used separation technique in the pharmaceutical industry. The attraction of the various modes of operation of CE to analysts is their complementarity to other more established methodology, in particular high-performance liquid chromatography. CE methods have been developed not only for the resolution of drug substances that vary widely in their structure, size and stereochemistry, but also for the determination of the physico-chemical constants of analytes, such as pK a and isoelectric point (pI) values, binding and complexation constants, and octanol-water partition coefficients.