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The effect of surfactants on the electrochemical determination of dexamethasone at an edge plane pyrolytic graphite electrode (EPPGE), modified with single-walled carbon nanotubes (SWNT) has been investigated. The unique electrocatalytic properties of SWNT along with the synergistic adsorption of CTAB on SWNT lead to sensitive voltammetric response of dexamethasone with the reduction peak at ca. À1195 mV. The limit of detection and sensitivity of dexamethasone is estimated to be 9.1 10 À10 M and 0.727 mA mM À1 respectively. The SWNT coated EPPGE had good stability and reproducibility. The analytical utility of the developed method was evaluated by applying it for sensing the drug in human body fluids and for the determination of dexamethasone content in several commercially available pharmaceutical preparations. A comparison of the observed results of proposed method with HPLC clearly indicates that the results of both the methods are in good agreement. The product obtained after the reduction of dexamethasone has also been characterized using 1 H NMR and carbonyl group at position 3 has been found to reduce. The method is instant, simple and accurate and can be easily applied for detecting cases of doping.