Several important figures of merit (migration time, efficiency, resolution, resolution per unit time, and electrophoretic selectivity) are quantitatively compared for the first time for conventional CZE and dual-opposite-injection CZE (DOI-CZE). Aspects of DOI-CZE relevant to the separation of organic and pharmaceutical ions (MW > 120 Da) are also discussed. Two new approaches to resolve the codetection of anions and cations, hydrodynamic flow-modified DOI-CZE and polarity reversal in combination with asymmetric detector window positioning, are compared with the method of preliminary transport, a variable procedure within sequential sample introduction, using a six-component sample of organic and pharmaceutical compounds. The advantages of DOI-CZE for the simultaneous analysis of organic/pharmaceutical anions and cations are illustrated in a direct comparison of conventional CZE and DOI-CZE for the separation of a ten-component mixture of pharmaceutical ions (five ionized acids and five ionized bases).