The glassy carbon electrode was fabricated with multifunctional bis-triazole-appended calix[4]arene and then used for the simultaneous detection of Zn(II), Pb(II), As(III), and Hg(II). Before applying the square-wave anodic stripping voltammetry, the sensitivity and precision of the modified electrode was assured by optimizing various conditions such as the modifier concentration, pH of the solution, deposition potential, accumulation time, and supporting electrolytes. The modified glassy carbon electrode was found to be responsive up to picomolar limits for the aforementioned heavy metal ions, which is a concentration limit much lower than the threshold level permitted by the World Health Organization. Importantly, the designed sensing platform showed anti-interference ability, good stability, repeatability, reproducibility, and applicability for the detection of multiple metal ions. The detection limits obtained for Zn(II), Pb(II), As(III), and Hg(II) are 66.3, 14.6, 71.9, and 28.9 pM, respectively. Copyright © 2019 American Chemical Society.