A highly sensitive molecularly imprinted electrochemiluminescence (MIECL) sensor was developed for detecting rifampicin (RIF) based on luminol@Co-MOF. Co-MOF had a significant enhancement of ECL signaling in the luminol-O system. Molecular imprinted polymers (MIPs) with the introduction of RIF provide new properties for the specific recognition of RIF. A noteworthy decrease in ECL intensity was observed with higher concentrations of RIF. Consequently, the ECL signal was controlled by RIF elution from and adsorption by the MIP, thus establishing a new method for RIF detection. Under optimal conditions, this sensor exhibited linear detection ranges of RIF between 1.0 × 10 mol L and 1.0 × 10 mol L, with a detection limit of 3.3 × 10 mol L (S/N = 3). The recoveries ranged between 98.1 and 106.0% in fish samples. This method can be used as a sensitive and rapid method to detect RIF in real samples.
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