Development of an efficient monitoring technology for rapid detection of toxic Pb(Ⅱ) ion in water environments is extremely important. Here, a novel and highly sensitive sensor was prepared using one-step calcination technique, based on Bi2O3 nanoparticles and carbonized metal–organic framework (MOF) nanocomposite. Scanning electron microscopy, transmission electron microscopy, contact angle and X-ray photoelectron spectroscopy characterization methods were used to analyze the morphology and structure of the prepared materials. Based on the electrical double-layer capacitance theory and Raman spectroscopy, changes to the active sites of different modified materials were investigated. Besides, differential charge densities and adsorption energies of the different modified materials in Zr-O clusters were calculated using density functional theory (DFT). A Bi2O3 and carbonized UIO-66-NH2 (Bi2O3/C-UIO-66-NH2) -modified glassy carbon electrode was used to detect Pb(Ⅱ) by differential pulse anodic stripping voltammetry. Under optimal experimental parameters, the developed electrochemical sensor has a wide linear range (2–130 μg/L) and a low detection limit (0.05 μg/L). Meanwhile, the sensor has excellent stability, repeatability, and anti-interference properties and has been successfully applied to detect Pb(Ⅱ) in actual water samples. The results of this paper show that our developed sensor an efficient and rapid sensor technology for monitoring lead in water environment.