A robust photoelectrochemical (PEC) sensor based on BiVO 4 has been successfully developed for the sensitive detection of the environmental estrogen-like compound bisphenol A (BPA). This sensor addresses the challenge of effectively immobilizing the photoactive material onto a supporting electrode. The BiVO 4 sensor is fabricated through a layer-by-layer approach using a hot spincoating method, providing an electrode with enhanced stability, compared to common spin-coating techniques, and is characterized using surface and electrochemical methods. The presence of OH − and SO 4 2− as active species significantly enhances the photocurrent on the PEC electrode surface by up to 100 times, enabling the detection of trace concentrations of BPA in various real matrices. The BPA sensing mechanism by the PEC sensor is investigated using confocal and spectrophotometric techniques. The electrode demonstrates excellent performance, allowing measurements in two linear concentration ranges of 0.01−10 μM and 10−120 μM, with a lower detection limit of 3.03 nM (3σ/m) for BPA. The sensor proves applicable to environmental water and human serum samples. Stability and reproducibility data indicate that the electrode maintains high reliability for at least 30 consecutive days. This material provides a readily accessible and durable solution for detecting BPA in diverse environmental and biological samples.