摘要： Sensitive but with simple, inexpensive detection of disease-related biomarkers in real biological samples is of quite necessity for early diagnosis and disease surveillance. We herein first introduced high-activity Fe3O4 nanozyme as signal amplifier to develop an ultrasensitive photoelectrochemical (PEC) immunoassay, which meanwhile has the distinct merits of both simplicity and low cost compared with previously reported enzyme-labeling PEC immunoassays. In the proposal, to illustrate and describe the PEC platform, prostate-specific antigen (PSA, Ag) was used as a target model. Specifically, ZnO nanorods (ZnO-NRs) grown vertically on a bare indium–tin oxide (ITO) electrode was deposited with ZnIn2S4 nanocrystals, producing ZnIn2S4/ZnO-NRs/ITO photoelectrode as the PEC matrix to modify capture PSA antibody (Ab1). Histidine-modified Fe3O4 (his-Fe3O4) nanozyme as signal amplifier was linked with signal PSA antibody (Ab2) to form his-Fe3O4@Ab2 conjugate, and was anchored through specific sandwich immunoreaction. The labeling his-Fe3O4 nanozyme acted as a peroxidase to induce the generation of the insoluble and insulating precipitation, resulting in an evident decrease in the photocurrent signal. On account of combined effects of high catalytic efficiency of the his-Fe3O4 nanozyme and excellent PEC properties of the ZnIn2S4/ZnO-NRs/ITO photoelectrode, ultralow detection limit of 18 fg/mL for target Ag detection was achieved. Besides, as high-activity his-Fe3O4 nanozyme has substituted natural enzyme as signal amplifier, simplicity and low cost of the PEC immunoassay was realized.