A rapid, simple, and practical method for the determination of four of the most used thyreostatic drugs (methimazole, 2-thiouracil, 6-methyl-2-thiouracil, and 6-propyl-2-thiouracil) using CE coupled to electrochemiluminescence detection has been established, based on the electrochemiluminescence enhancement of tris(2,2-bipyridyl)ruthenium(II) with these analytes. Parameters that affect separation and detection were optimized. Under the optimum experimental conditions, the four analytes could be well separated within 11 min at the separation voltage of 16 kV in a running solution containing 20 mM phosphate buffer (pH 9.0) and 1.0 × 10(-4) M Ru(bpy)(3)(2+), with a solution of 20 mM phosphate buffer (pH 12.0) containing 1.0 × 10(-4) M Ru(bpy)(3)(2+) in the electrochemiluminescence detection cell. The detection limits for methimazole, 6-methyl-2-thiouracil, 6-propyl-2-thiouracil, and 2-thiouracil were 0.1, 0.05, 0.05, and 0.01 μM, respectively. The proposed method was applied to analyze these drugs in spiked animal feed samples. The recoveries were 88.2∼99.0 and 86.4∼98.7% for the intraday and interday analyses, respectively. The RSDs were 2.7∼4.8 and 1.8∼5.0% for the intraday and interday analyses, respectively. The results demonstrate that the proposed method has promising applications in the detection of thyreostatic drugs in animal feeds.