Amitriptyline, doxepin and chlorpromazine are often used as psychotropic drugs in treatment of the various mental diseases, and are also partly excreted by kidney. This work developed a simple, selective and sensitive method for their simultaneous monitoring in human urine using capillary electrophoresis coupled with electrochemiluminescence (ECL) detection based on end-column ECL reaction of tris-(2,2'-bipyridyl)ruthenium(H) with aliphatic tertiary amino moieties. Acetone was used as an additive to the running buffer to obtain their absolute separation. Under optimized conditions the proposed method displayed a linear range from 5.0 to 800 ng mL(-1) for the three drugs with the correlation coefficients more than 0.995 (n=8). Their limits of detection were 0.8ngmL(-1) (3.6fg), 1.0ngmL(-1) (4.5fg) and 1.5ngmL(-1) (6.8fg) at a signal to noise ratio of 3, respectively. The relative standard deviations for five determinations of 20ngmL(-1) amitriptyline, doxepin and chlorpromazine were 1.7%, 4.2% and 3.6%, respectively. For practical application an extract step with 90: 10 heptane/ethyl acetate (v/v) was performed to eliminate the influence of ionic strength in sample. The recoveries of amitriptyline, doxepin and chlorpromazine at different levels in human urine were between 83% and 93%, which showed that the method was valuable in clinical and biochemical laboratories for monitoring amitriptyline, doxepin and chlorpromazine. (c) 2006 Elsevier B.V. All rights reserved.