Selective anodic stripping voltammetry of trace metal ions in a mixture solution with another interfering metal was developed based on Fick's law concerning the diffusion profile of interfering metals at the electrode surface after electrolysis treatment. A boron-doped diamond film was used as the sensing electrode, while a perforated carbon sheet was used for the interference-depleting electrode. The influence of the electrode distance and the time of electrolysis on the formation of the diffusion profile was studied. As a working model, the detection of cadmium with copper interference was investigated. The advantage of the method in comparison to general electrolysis was also discussed. The method offers a new perspective for improving the selective detection of metal ions by analyzing the diffusion profiles of the interfering species at the surface of electrodes.