Agricultural products are usually susceptible to mycotoxin contamination; the rapid and reliable detection of mycotoxins at the early stage is crucial for food safety. Here, a photocurrent-polarity-switchable cathodic photoelectrochemical (PEC) aptasensing platform was established for fumonisin B1 (FB1) analysis based on a novel ZnS/Bi2S3/Bi2Ti4O11 (BTO) electrospun nanoheterojunction. Introducing S/Zn sources on Bi4Ti3O12 electrospun nanofibers induced the component transformation of Bi4Ti3O12 into BTO to generate ZnS/Bi2S3/BTO with double Z-scheme heterojunctions, thereby switching from anodic to cathodic photocurrent. On the photocathodic aptasensing interfaces of ZnS/Bi2S3/BTO, the FB1 aptamer-modified Au NPs/NiCo2O4 as peroxidase-like mimics accelerate the oxidation of 4-chloro-1-naphthol in a H2O2 environment to produce insoluble precipitates, quenching the photocathodic current with a 77.6% quenching efficiency. After incubation with FB1, the specific binding between FB1 and the aptamer could effectively reduce the catalytic sites of Au NPs/NiCo2O4, resulting in the recovery of photocathodic current signals for the detection of FB1 with a linear range of 0.5 pg/mL-1000 ng/mL and a detection limit of 0.385 pg/mL. In a word, this work for the first time synthesized the novel ZnS/Bi2S3/BTO double Z-scheme electrospun heterojunctions as highly active photocathodic materials, offering a new perspective in the advancing polarity-switchable PEC bioanalysis.