Objective To establish a novel method for simultaneous determination of three ingredients (codeine phosphate, brompheniramine maleate and ephedrine hydrochloride) in compound codeine phosphate solution by using capillary electrophoresis (CE) coupled with electrochemiluminescence (ECL). Methods Based on enhanced ECL intensity of tris (2,2′-bypyridine) ruthenium (Ⅱ) with codeine phosphate, brompheniramine maleate and ephedrine hydrochloride, as well as the linear correlation between enhanced sensitivity intensity and drug concentration, Parameters affecting separation and detection were optimized. Results Under the optimized conditions, we determined the linear range, regression equation and detection limit for the three ingredients. The relative standard deviation of ECL intensity for twelve consecutive injections of 1.0×10~(-5)kg/L standard sample of three kinds of drug was 2.89% for codeine phosphate, 3.76% for brompheniramine maleate and 3.32% for ephedrine hydrochloride, respectively. Satisfactory results were obtained without interference from sample matrixes. Conclusion The method was successfully applied to the determination of three ingredients in oral solution of compound codeine phosphate, with the recovery rate of 100.4% for codeine phosphate, 101.9% for brompheniramine maleate and 99.8% for ephedrine hydrochloride.