The detection of bisphenol A (BPA) is very important for public health and environmental monitoring. In this work, BPA was found to be able to significantly quench the electrochemiluminescence (ECL) of the Ru(bpy) 3 2+ /2-(dibutylamino)ethanol (DBAE) system. Molecularly imprinted polymer was synthesized as solid-phase extraction sorbents, which were used for the selective extraction and purification of BPA. Under optimal conditions, the inhibited ECL intensity versus the logarithm of the concentration of BPA was in good linear relationship over a concentration range from 2.2 × 10 −10 to 1.1 × 10 −7 mol/L. The limit of detection was 4.5 × 10 −11 mol/L (S/N = 3). The developed method was successfully applied for determination of BPA in river water with high sensitivity and reliability. Further, a possible mechanism for the quenching effects of the Ru(bpy) 3 2+ /DBAE system by BPA was also proposed.