The performance of a recently introduced capillary ion-exchange chromatography system was explored. Experiments were conducted in isocratic mode with a commercial capillary anion-exchange column (id = 0.4 mm, L = 15 cm) using a five-anion standard mixture. The achieved results were compared to the performance of a standard bore ion-exchange system (id = 4 mm, L = 15 cm), which was considered as a reference. The first-generation capillary columns exhibited a minimal reduced plate-height value below two witnessing a good packing quality and system performance. However, compared to the standard bore system the capillary system displayed an increased apparent C-term which could be due to a difference in packing morphology and/or possible external band-broadening contributions. For fast separations, the standard bore system outperformed the capillary system, while for complex separations both systems performed nearly equally well. In addition, the retention characteristics of the capillary system were investigated. To illustrate the suitability of the capillary system, the analysis of real-world water samples originating from two local Belgian rivers was demonstrated.