A new sensitive electrochemical sensor was fabricated based on a layer by layer process. In this process the glassy carbon electrode (GCE) is first coated by a thin film of multiwalled carbon nanotubes (MWCNTs). In the next step, the electropolymerization of pyrrole in the presence of Nitrazine Yellow (NY) as a dopant anion is performed on the surface of the MWCNTs precoated electrode. The electrochemical response characteristics of the modified electrode toward naltrexone (NTX) were studied by means of linear sweep voltammetry (LSV). A remarkable increase (~19 times) was observed in the anodic peak current of NTX on the surface of the modified electrode relative to the bare GCE. The effects of experimental parameters on the electrode response such as, drop size of the cast MWCNTs suspension, pH of the supporting electrolyte, accumulation conditions and the number of cycles in the electropolymerization process were investigated. Under the optimum conditions, the modified electrode showed a wide linear response to the concentration of NTX in the range of 4.0 10À5 mol L À1 with a detection limit of 12 nmol L
À1. The prepared sensor exhibited high sensitivity, stability and good reproducibility for the determination of NTX. This sensor was successfully applied for the accurate determination of trace amounts of NTX in pharmaceutical and clinical preparations.