A new type of temperature‐responsive electrochemical sensor was constructed based on a glass carbon electrode modified by the composite containing temperature‐responsive polymer polystyrene‐poly N, N‐diethyl acrylamide‐polystyrene (PS‐PDEA‐PS) and fullerenes‐carboxylate multi‐walled carbon nanotubes (C60‐MWCNTs). The sensor was used for the electrochemical detection of catechol (CC). When the temperature is higher than the critical temperature (LCST) of PS‐PDEA‐PS, the electrochemical behavior of CC can be detected, which it is in the “on” state. When the temperature is lower than LCST, the composite modified film is in the “off” state and the electrochemical behavior of CC was not detected. Under the best experimental conditions, the sensor has a good detection range for catechol from 4.0 to 135.0 μM, with a LOD of 1.45 μM. In addition, the proposed sensor has good stability and reproducibility, and was successfully applied to the determination of catechol in real tap water.