An ultrasensitive molecularly imprinted polymer-photoelectrochemical (MIP-PEC) sensing platform has been successfully fabricated for the detection of diflubenzuron (DBZ) under visible-light irradiation. The noval photoactive material was a ternary Bi2S3/BiVO4/TiO2 nanotube arrays (BVT) heterojunction, grown in-situ on a Ti substrate. The distinct architecture of BVT featured BiVO4 nanoparticles anchored onto TiO2 nanotube arrays and wrapped by Bi2S3 nanofibers. This innovative design, coupled with the aligned energy bands of BVT, significantly boosted visible-light absorption, and photo-induced charge separation and transfer, leading to an enhanced photocurrent response surpassing that of binary and single-component systems. The sensing platform displayed remarkable sensitivity and a broad detection range for DBZ with a linear range of 0.01–1000 ng mL−1 and a limit of detection of 1.25 pg mL−1. Its selectivity was further validated by comparable photocurrent responses in the presence of interfering substances, highlighting its accuracy in detecting DBZ in complex matrices. Additionally, the sensing platform demonstrated excellent stability and reproducibility, ensuring reliable results over multiple measurements. Evaluation of the sensing platform in real samples, including tap water and apples, has confirmed its high accuracy with recovery rates between 94.4 % and 103.4 %. Therefore, this visible-light-driven MIP-PEC sensing platform exhibits considerable potential for application in ultrasensitive detection of DBZ. This work offers novel insights into the in-situ preparation of high-performance sensors for applications in food safety and environmental monitoring.