The detection of bisphenol A (BPA) in wastewater is imperative due to its significant environmental impact. In this research, we devised an electrochemical sensor utilizing photoinduced calcium deposition on molecularly imprinted TiO2 (MI–Ca–TiO2) for the sensitive and selective detection of BPA. This novel approach combines Ca-doping and molecular imprinting in TiO2, achieving enhanced conductivity and selective binding sites for BPA. The MI–Ca–TiO2 sensor demonstrated linear detection ranges from 0.01 to 20 μM and a low detection limit of 6.0 nM. Consistent repeatability was observed across various batches of MI–Ca–TiO2, indicated by a relative standard deviation of 0.8%. Notably, the sensor maintained a high differential pulse voltammetry response even after prolonged storage in a refrigerator. Moreover, in the presence of a 100-fold higher concentration of analogous or interfering ions, the MI–Ca–TiO2 nanosheets exhibited a marked current response, affirming their efficacy in BPA detection. These findings indicate the potential of the MI–Ca–TiO2 sensor as a simple, cost-effective, and efficient tool for detecting BPA in water.