AbstractCarcinoembryonic antigen (CEA) was used as the model, an ultrasensitive label-free photoelectrochemical immunosensor was developed using 2D TiO₂ nanosheets and carboxylated graphitic carbon nitride (g-C₃N₄) as photoactive materials and ascorbic acid as an efficient electron donor. 2D TiO₂ nanosheets was sythsized by surfactant self-assembly method and proved to have higher photoelectrochemical signals than TiO₂ nanoparticles. Firstly, carboxylated g-C₃N₄ could be attached to 2D TiO₂ nanosheets through the bond formed between carboxyl group of carboxylated g-C₃N₄ and TiO₂. And the photocurrent of g-C₃N₄/TiO₂ drastically enhances compared to carboxylated g-C₃N₄ and TiO₂. Then, antibody of CEA was bonded to TiO₂ through the dentate bond formed between carboxyl group of anti-CEA and TiO₂, leading to the decrease of the photocurrents. As proven by PEC experiments and electrochemical impedance spectroscopy (EIS) analysis, the fabrication process of the immunosensor is successful. Under the optimal conditions, the intensity decreased linearly with CEA concentration in the range of 0.01~10 ng/mL. The detection limit is 2.1 pg/mL. The work provides an effective method for the detection of tumor markers and can be extended for the application in food safety and environmental monitoring analysis.