In this study, a porous molecularly imprinted electrochemical sensor was successfully fabricated for the selective assay of bisphenol S (BPS) by introducing N-methacryloyl-L tyrosine functional monomer. The molecularly imprinted polymer (MIP)-based sensor (MA-Tyr @MIP/GCE) was prepared via photopolymerization on the glassy carbon electrode and subsequently characterized by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and Fourier-transform infrared spectroscopy (FTIR). The analytical performance of the sensor was evaluated via CV and differential pulse voltammetry (DPV) measurements. Under the optimized conditions, the rebinding experiment demonstrated that the peak current of the porous MIP-based sensor obviously decreased with the increase of BPS concentration in the concentration range of 1-10 fM. Therefore, the detection limit was determined as 0.171 fM. It should be underlined that MA-Tyr @MIP/GCE exhibited high sensitivity and excellent selectivity because MA-TyrMA-Tyr @MIP/GCE sensor has a higher imprinting factor (IF) toward BPS in respect to competitive analogs, i.e., bisphenol A, bisphenol B, and bisphenol F. The practical application of the sensor also showed good reproducibility and stability for the detection of BPS in human serum and water samples. These results showed MA-Tyr @MIP/GCE successfully applied for the selective recognition of BPS in biological and water samples with high sensitivity and excellent selectivity.