Tert-butylhydroquinone (TBHQ) is widely used to increase the stability of food products; however, it is considered to be a highly unsafe preservative ingredient that has caused serious damage to human health. Thus, in this paper, a novel molecularly imprinted electrochemical sensor was designed for ultrasensitive, and selective detection of TBHQ in edible oils. The sensor was based on the molecularly imprinted polymer (MIP) synthesized with multiwalled carbon nanotube (MWCNT), and gold nanoparticle (GNP), as the coating materials, o-phenylenediamine (o-PDA) as the functional monomer, and TBHQ as the template molecule. The electrochemical behavior of MIP/GNP/MWCNT/GCE was studied using several electrochemical methods, which showed a low detection limit of 5 nM. Furthermore the sensor demostrated excellent stability, selectivity, repeatability, and reproducibility. It was successfully used to detect TBHQ in edible oils, with recoveries ranging from 98.44% to 102.09% and relative standard deviations (RSDs) of less than 2.16%, indicating that TBHQ detection in actual samples is both possible and accurate.