In this work, N-doped hollow porous carbon spheres (N-HPCSs) were synthesized by silicon dioxide template-assisted polybenzoxazine (PB) coating strategy. The prepared N-HPCSs have a smooth hollow ball structure surrounded by a well-defined porous shell. Combining with in-situ plating of Bi film, the N-HPCSs were further fabricated a sensitive electrochemical platform for determination trace levels of Cd(II) by differential pulse anodic stripping voltammetry (DPASV). Under the optimized conditions, the Bi-N-HPCSs based sensor displays a linear response to Cd(II) over the range of 0.5gL(-1) to 150gL(-1). Meanwhile, the limit of detection (LOD, S/N=3) is estimated to be around 0.16gL(-1) for Cd(II), which is 31 times lower than the safety values set by United States Environmental Protection Agency (EPA) for the drinking water. Moreover, the proposed method was successfully applied to detection of Cd(II) in tap water and lake water, and the analytical results of the presented method are agreed well with inductively coupled plasma-mass spectrometry (ICP-MS) data. Due to the excellent analytical performance, the fabricated electrode is promised for future development in monitoring of cadmium pollution in the environment.