A new homemade ECL (electrochemiluminescence) system, including essentially a luminescence spectrometer coupled with an electrochemical analysis system was used for the determination of doxylamine succinate as a co-reactant of Tris(2,2-bipyridyl)ruthenium(II) complex which emits light at 610 nm. Under the optimum condition, the linearity of the calibration curve was from 1.00×10−6 to 3.00×10−4 mol L−1 with a correlation coefficient of 0.9990 and a detection limit of 3.00×10−7 molL−1. The RSD ranged from 0.97% to 2.60%. The applicability of the proposed homemade instrument was illustrated in the determination of doxylamine succinate in human urine. The recoveries of doxylamine were found to be in the range from 97.50% to 98.67%. This homemade instrument could be used for the quantification of pharmaceuticals without needing derivatives and is applicable for pharmaceuticals without the use of chromophore group. The ECL detection of doxylamine succinate in solution is better than other instruments such as the spectrophotometric method and the HPLC one. Also, this homemade instrument can be used to monitor doxylamine succinate and other pharmaceuticals containing tertiary amine groups in the urine without any significant interference for signal achievement.