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A new electrochemical sensor based on the multiwalled carbon nanotube (MWCNT)/Li4Ti5O12-modified glassy carbon electrode for determination of bisphenol A (BPA) was developed by modifying the surface of a glassy carbon electrode with the prepared composite Li4Ti5O12/MWCNTs. The morphology and structure of the composite were characterized by infrared spectroscopy and scanning electron microscope. The obtained electrochemical sensor Li4Ti5O12/MWCNTs/GCE takes advantages of large specific surface area of the Li4Ti5O12 nanostructure, excellent adsorption properties, and electrochemical properties of MWCNTs. Under optimal conditions, the response of the proposed sensor to BPA was linear in the BPA concentration range from 1.0 × 10−7 to 1.0 × 10−5 mol L−1 and the detection limit was of 7.8 × 10−8 mol L−1 according to the 3σ rule. The results revealed that the newly developed sensor exhibited high sensitivity and selectivity, excellent electrochemical performance, and fast response to BPA, allowing it to be used for the detection of BPA in actual samples.