The present study reports the fabrication of a carbon nanotube/Nafion composite film (MWNT/Nafion)-modified glassy carbon electrode (GCE) along with its excellent performance in the analysis of Pb 2+ (favorable catalytic activity, large surface area, high cation exchange capacity, and strong adsorption ability). The stripping peak current of Pb 2+ was greatly increased at the MWNT/Nafion-coated GCE compared with the bare and Nafion-coated GCEs. The optimization of different parameters was also carried out, including optimization of the accumulation time, accumulation potential, supporting electrolyte, and MWNT/Nafion suspension volume. Therefore, our developed electrode can be used in the analysis of Pb 2+ in real hot spring water samples.