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The present work reports a newly developed square wave anodic stripping voltammetry (SWASV) methodology using novel gold nanostar–modified screen-printed carbon electrodes (AuNS/SPCE) and modified Britton-Robinson buffer (mBRB) for simultaneous detection of trace cadmium(II), arsenic(III), and selenium(IV). During individual and simultaneous detection, Cd2+, As3+, and Se4+ exhibited well-separated SWASV peaks at approximately − 0.48, − 0.09, and 0.65 V, respectively (versus Ag/AgCl reference electrode), which enabled a highly selective detection of the three analytes. Electrochemical impedance spectrum tests showed a significant decrease in charge transfer resistance with the AuNS/SPCE (0.8 kΩ) compared with bare SPCE (2.4 kΩ). Cyclic voltammetry experiments showed a significant increase in electroactive surface area with electrode modification. The low charge transfer resistance and high electroactive surface area contributed to the high sensitivity for Cd2+ (0.0767 μA (0.225 μg L−1)−1), As3+ (0.2213 μA (μg L−1)−1), and Se4+ (μA (μg L−1)−1). The three analytes had linear stripping responses over the concentration range of 0 to 100 μg L−1, with the obtained LoD for Cd2+, As3+, and Se4+ of 1.6, 0.8, and 1.6 μg L−1, respectively. In comparison with individual detection, the simultaneous detection of As3+ and Se4+ showed peak height reductions of 40.8% and 42.7%, respectively. This result was associated with the possible formation of electrochemically inactive arsenic triselenide (As2Se3) during the preconcentration step. Surface water analysis resulted in average percent recoveries of 109% for Cd2+, 93% for As3+, and 92% for Se4+, indicating the proposed method is accurate and reliable for the simultaneous detection of Cd2+, As3+, and Se4+ in real water samples. [ABSTRACT FROM AUTHOR]