The behavior of chlordiazepoxide has been studied using dc-polarography at dropping mercury electrode (DME) and cyclic voltammetry at glassy carbon electrode (GCE). In Britton-Robinson buffers, the drug developed three reduction irreversible waves in acidic solutions, and only two waves in alkaline media. The adsorptive stripping voltammetric behavior of chlorodiazepoxide was studied at GCE, and a sensitive voltammetric method was evaluated applying linear-sweep mode for quantitative determination of the drug in pure form and commercial tablets. A linear relationship between peak current and drug concentration was obtained in the concentration range 2x10-7 to 5x10-6 mol l-1 of the drug at pH = 4.0, with a detection limit of 5x10-8 M. The drug was determined in capsules with a percentage recovery of 100.65 ± 1.83 (n=5).