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In this study, a rapid and sensitive method using capillary electrophoresis with indirect UV detection and minimal sample pretreatment was developed and evaluated to analyze choline chloride in oilfield process water samples. To improve peak resolution and separation of choline chloride from other cations present in the samples, the addition of a cationic visualization agent in the background electrolyte, imidazole, and a complexing agent, 18-crown-6, were introduced. Other factors affecting separation and sensitivity were also investigated. Under optimized conditions, choline chloride was baseline separated (<7 min) from common cationic adulterants in commercial choline chloride products with a peak resolution of >1.5 between adjacent peaks. The limits of detection (signal-to-noise ratio = 3) and quantitation (signal-to-noise ratio = 10) were 14.7 and 48.9 mg L−1, respectively. The peak area and migration time’s intraday and interday precision (percent RSD) were all <15%, and the recoveries ranged from 79.4% to 115.2% at different spiking levels. Finally, statistical (Student’s t-test) comparison of the choline chloride content data of oilfield process water samples from the proposed capillary electrophoresis (CE) method compare favourably with traditional methods such as liquid chromatography – mass spectrometry (LC–MS) and Reinecke salt gravimetry.