The utilization of bismuth as a sensing material for the detection of heavy metal ions has gained significant attention due to its exceptional interfacial activity and selective absorption properties. However, it also poses challenges in terms of agglomeration and its inferior electrical conductivity during the synthesis process. This paper employed a facile in situ synthesis and electrodeposition approach to uniformly grow a bismuth film on a conductive carbon cloth, designated as Bi/Ag@CC. The Bi/Ag@CC electrode material exhibited benign electrochemical properties, enabling its application for detecting Pb2+ in tap water and lake water samples. Furthermore, this work investigated the impact of electrochemical parameters, including electrolyte pH, deposition potential and pre-enrichment time, on the detection performance. The results demonstrated the sensor’s wide linear range (from 20 to 400 ppb) and detection limits (0.15 ppb) for heavy metal ion detection, along with excellent anti-interference capabilities and satisfactory repeatability, with an RSD of less than 2.31% (n = 6). This paper offers a novel strategy for positioning the bismuth-based composite as a promising candidate for practical electrochemical sensing applications.