The popularity of capillary electrophoresis (CE) as a separation technique has been established over the years. CE offers the advantages of high resolution, high separation efficiency, fast approaches of method development, a range of operational modes and low consumption of reagents. The strategy employed here for the development of chromatographic separations involved the utilization of experimental designs, multi-linear regression and response surface methodology to build empirical models that related the chromatographic quality to the factors influencing the separation. Separation of Nitrofuran antibiotics (NFAs) and their metabolites (NFMs) by using micellar electrokinetic capillary chromatography was successfully completed. The best conditions found to give optimum resolution from the optimization study was pH 9.0, 80 mM SDC concentration, 16 kV with running buffer consisting of 20 mM borate and 20 mM phosphate concentration using a 73 cm x 75 ƒÝm column, resulting in completely resolved NFAs and NFMs within 16 min. It is interesting that all the compounds can be reliably separated with the one mixture, and single CE condition. Whilst all antibiotics have shorter migration time than their respective derivatised metabolites, as a group apart from nitrofurantoin the antibiotics elute before the metabolites. The analytical figures of merit for CE analysis exhibited excellent reproducibility of absolute and relative migration times, and acceptable reproducibility of relative response areas. Successful separation of metabolite derivatives was achieved when the developed method was applied to a spiked prawn sample. The chiral separation of Triadimenol was successfully completed using micellar electrokinetic capillary chromatography. The best conditions found to give optimum resolution from the optimisation study were pH 6.0, 20% methanol, 50 mM SDS concentration, 18 kV with running buffer consisting of 20 mM borate and 20 mM phosphate concentration using a 64.5 cm x 50 ƒÝm column, resulted in baseline resolution of all Triadimenol isomers within 18 min. The optimised separation conditions were applied to a blank grape sample and to a spiked grape sample. No peaks were observed in the blank grape sample whereas the spiked grape sample had two diastereoismer peaks with poor detection sensitivity. Increase in detection sensitivity is necessary to determine the possibility of resolution of all the isomers of Triadimenol, in the spiked grape sample and the blank. Online preconcentration techniques were attempted to for Triadimenol isomer separation. When using online preconcentration technique of sweeping, a 30-fold increase in detection sensitivity of Triadimenol was observed compared to MEKC mode. However enantiomer separation was not possible with sulfated-£]-CD chiral selector. The best conditions were found to be pH 2.5, 50 mM SDS concentration, -20 kV with running buffer consisting of 20 mM phosphate concentration, using a 64.5 cm x 50 ƒÝm column, resulting in diastereoisomer separation within 8 min. Final stage of the project was to create stationary phase beds in capillaries and micro-channels that could be removed and re-created, thus providing a fresh stationary phase. The replaceable stationary phase (RSP) can be used as an operating mode of CE/CEC. Preparation of reversible stationary phase (RSP) inside the capillary column was successfully performed using low methoxy pectin (LMP). LMP renders a capability of reversible thermogelation. Electroosmotic flow (EOF) and sufficient hydrophobicity of LMP gel allow separation of analyates. The porosity of LMP RSP was adequate to support EOF. Successful separation with good reproducibility of areas and migration times was obtained for Caffeine, Aspartame, Benzoic acid, Saccharine (CABS) mixture and NFAs. After performing continuous analyses, the aging of RSP was observed. Temperature was the ¡¥switch¡¦, which applied to remove aged RSP. RSP was recreated for further analysis of analytes. RSP was UV transparent, capable of handling various analytes and diff erent buffer electrolytes including aqueous-organic solvents.