A label-free addressable photoelectric immunosensor array was designed for the detection of amyloid β-proteins based on magnetic separation and self-calibration strategies. In this paper, Na2Ti6O13 with a flower-like morphology was prepared by the hydrothermal method; after continuously combining Fe3O4 and CdS, it was endowed with magnetism and better photoelectric activity. Subsequently, a series of reactions occurred in the solution, and the magnetic separation method was used to enrich the target. On the other hand, the ITO glass was separated into eight sites (2 × 4) using magnets, and a light shield was utilized to prevent light exposure, resulting in addressable and continuous detection. After the uniform preparation of magnetic photoelectric materials and precise control of testing conditions, the relative errors among different sites have been effectively reduced. Moreover, incorporating a self-calibration strategy has allowed the sensor array to achieve greater accuracy. The proposed photoelectrochemical biosensor exhibits a good relationship with amyloid β-protein ranging from 0.01 to 100 ng mL-1 with a limit of detection of 1.1 pg mL-1 and exhibits excellent specificity, reproducibility, and stability.