The electrochemical behavior of nicotine in alkaline media was studied using a boron doped diamond (BDD) surface as the working electrode. In order to establish the pH dependence and to gain information about the mass transport of the species, cyclic voltammetry studies were carried out in a 0.1 mol L−1 BR (Britton‐Robinson) buffer in the presence of 1.0×10−3 mol L−1 nicotine. The optimum pH value was 8 and the mass transport was controlled by diffusion of the species. The square wave voltammetry technique was used to determine the electroanalytical parameters such as frequency, amplitude, and scan increment. After optimization, an analytical curve was constructed. The limits of detection and quantification were 0.50 and 1.66 mg L−1, respectively. Theoretical calculations indicate that the probable oxidation site on the nicotine molecule was the nitrogen atom denoted “11 N” and a speculation about the reaction mechanism was proposed. Finally, an experiment using a real sample (cigarette tobacco) ...