Our research addresses the pressing need for environmental sensors capable of large-scale, on-site detection of a wide array of heavy metals with highly accurate sensor metrics. We present a novel approach using electrochemically polished (ECP) carbon screen-printed electrodes (cSPEs) for high-sensitivity detection of cadmium and lead. By applying a range of techniques, including scanning electron microscopy, energy-dispersive spectroscopy, Raman spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry, we investigated the impact of the electrochemical potential scan range, scan rate, and the number of cycles on electrode response and its ability to detect cadmium and lead. Our findings reveal a 41 ± 1.2% increase in voltammogram currents and a 51 ± 1.6% decrease in potential separations (n = 3), indicating a significantly improved active electrode area and kinetics. The impedance model elucidates the microstructural and electrochemical property changes in the ECP-treated electrodes, showing an 88 ± 2% (n = 3) decrease in the charge transfer resistance, leading to enhanced electrode electrical conductivity. A bismuth-reduced graphene oxide nanocomposite-modified, ECP-treated electrode demonstrated a higher cadmium and lead sensitivity of up to 5 ± 0.1 μAppb⁻¹cm⁻² and 2.7 ± 0.1 μAppb⁻¹cm⁻² (n = 3), respectively, resulting in sub-ppb limits of detection in spiked deionized water samples. Our study underscores the potential of optimally ECP-activated electrodes as a foundation for designing ultrasensitive heavy metal sensors for a wide range of real-world heavy metal-contaminated waters.