To improve reproducibility, stability and sensitivity, a bismuth (Bi) thin film was coated on glassy carbon (GC) substrates which surfaces were modified with a porous thin layer of polyaniline (PANI) via multipulse potentiostatic electropolymerization to form Bi/PANI/GC electrodes (Bi/PANI/GCEs). The Bi/PANI/GCEs were used successfully for simultaneous detection and determination of Cd 2þ and Pb 2þ ions, and various parameters were studied with reference to square wave anodic stripping voltammetric (SWASV) signals. The experimental results depicted that the environment-friendly Bi/PANI/GCEs had the ability to rapidly monitor trace heavy metals even in the presence of surface-active compounds.