Generally, the photoanodic photoelectrochemical (PEC) immunoassay method has an outstanding photocurrent and low detection limit, but its poor anti-interference ability in the detection of real samples restricts its performance. The photocathode immunoassay method has an excellent ability to see interference in actual sample detection, but it has its own defect in that the photocurrent is not obvious. Here, a promising new cathodic PEC immunosensing platform is reported, which integrates a photocathode and photoanode. The photoanode and photocathode are WO3/Mn:CdS composite modified and reduced graphene oxide (RGO) modified indium tin oxide (ITO) electrodes, respectively. In addition to an excellent PEC response, the immunosensor constructed by the integrating the photoanode and photocathode also has good anti-interference ability in actual sample analysis. The constructed immunosensor achieves accurate detection of NSE with a range from 5.0 pg/mL to 20 ng/mL, and the limit of detection (LOD) is 1.2 pg/mL. The proposed immunoassay method has good stability, selectivity and reproducibility. Moreover, it introduces new ideas for the construction of PEC immunosensors.