Large-scale bunch-like bismuth (Bi) nanostructures were the first time to be synthesized via two-step electrochemical deposition. The growth mechanism of the nanostructures was discussed. Such a designed bunch-like Bi electrode has high sensitivity to detect the heavy metal ions due to its unique three-dimensional structures and strong ability of adsorbing the heavy metal ions. The bunch-like Bi electrode's detection of heavy metals was statically performed using anodic stripping voltammetry (ASV). The detection in the Pb(II) concentration range of 2.5-50 mug/l was also performed. Based on the experimental results, this bunch-like Bi electrode can be considered as an interesting alternative to common mercury electrodes and bismuth film electrodes for possible use in electrochemical studies and electroanalytical applications.