ß-blockers are one group of the most widely used drugs to treat heart failure, high blood pressure and abnormal heart rhythms. The purpose of this study was to develop capillary columns of stationary phases from molecular imprinting and sol-gel methodology for the determination of ß-blockers prior to capillary electrochromatography (CEC) analysis. In the first part of the study, molecularly imprinted organic based polymers (MIPs), silica-based molecularly imprinted polymers (SMIPs) and silica-based sorbents were developed, characterized and utilized for sorption of metoprolol, an example of ß-blockers. The three different types of sorbents were studied as stationary phases of capillary column. Critical parameters on sorption of metoprolol were investigated. In the second part, the subsequent studies were concentrated on the preparation new capillary column for separation and determination of metoprolol for CEC analysis. The performance of three different types of sorbents was compared. Molecularly imprinted organic polymers show higher sorption and selectivity towards metoprolol as compared with the other sorbent types. The preparation of stationary phases of capillary columns with molecular imprinted organic polymers was proposed for determination of metoprolol prior to CEC analysis. After stationary phase optimization studies, an open tubular column was prepared and its performance was examined.