Lead is very hazardous, as it is present in environmental samples, and it causes severe health problems affecting neurological, cardiac, genital, and mental illnesses owing to exposure to even a trace amount. The achievement of selective detection of Pb2+ ions is challenging due to interfering relevant metal ions. Hence, in this work, we have synthesized the Nitrogen and Sulphur N and S-doped reduced graphene oxide (NS-rGO) and fabricated it using electrophoretic deposition (EPD) in glassy carbon electrode (GCE) and Bi film deposition (Bi/EPD-NS-rGO/GCE) for selective detection of Pb2+ ions. The synthesized materials were characterized to confirm their functionalities, elemental analysis, and morphology. Further, the electrochemical behaviours were also carried out through Cyclic Voltammetry (CV) and Electrochemical Impedimetric spectroscopy (EIS) studies. The above-modified electrodes were utilized for selective detection of Pb2+ in the presence of Cd2+ ionsusing the differential pulse anodic stripping voltammetry (DPASV) method. The electrode modified with NS-rGO using the EPD method, along with a thin film of Bi that was electrodeposited, has better and more selective catalytic activity for sensing Pb2+ ions. The linear working response was found to be in the range of 100–2200 nM with a limit of detection (LOD) of 0.180 nM and verified as 144 times lower than the recommended level (26 nM) by World Health Organization (WHO) and United States Environmental Protection Agency (USEPA). The developed sensor was further applied to the selective detection of Pb2+ ions in tap water and river water, and it shows good recovery. The Bi/EPD-NS-rGO/GCE will explore a new pathway for the simple and selective detection of Pb2+ ions.