An electrochemical study of the doxazosin oxidative process at carbon paste electrodes using different voltammetric techniques has been carried out. The process is irreversible and controlled by adsorption, giving rise to an oxidation wave around 1.0 V in citric acid-citrate buffer (pH 3.0). A mechanism based on the oxidation of the amine group is postulated. Two methods based on adsorptive st:ripping (AdS) of doxazosin at the C-8-modified carbon paste electrode (C-8-MCPE), before its voltammetric determination, are studied, using differential pulse voltammetry (DPV) and square wave voltammetry (SWV) as redissolution techniques. By means of AdS-DPV and C-8-MCPE, doxazosin can be determined over the 1.0 x 10(-9) to 3.0 x 10(-8) mol L-1 range with a variation coefficient of 2.2% (2.0 x 10(-8) mol L-1) and a limit of detection of 7.4 x 10(-10) mol L-1. If AdS-SWV is used, a linear range from 1.0 x 10(-9) to 4.0 x 10(-8) mol L-1 is obtained, the variation coefficient being 2.8% (2.0 x 10(-8) mol L-1, and the limit of detection reached 7.7 x 10(-10) mol L-1. The AdS-DPV procedure was applied to the determination of doxazosin in urine and formulations.