This research describes a nanocomposite coating consisting of polytyramine (PTy) and graphene oxide nanosheets@copper nanoparticles (GO@CuNPs) which is synthesized through one-step electropolymerization mode on the surface of a steel wire. The performance of the PTy/GO@CuNPs nanocomposite was evaluated as a new polar coating for solid-phase microextraction of bisphenol A and its analogs in canned drinks and foods, canned pet foods and empty cans preceding to gas chromatography-mass spectrometry. In order to attain efficient nanocomposite coating, the operative parameters related to the electrochemical approach and the microextraction implementation were considered exhaustively and optimized. Under the optimized experimental mood, the calibration curves of the target analytes were plotted with limits of detection ranges from 4.0 to 8.0 ng L−1. The relative standard deviations using a single fiber and three fibers were below 7.4% and 11.2%, respectively. Besides, the recoveries of this method for real samples were higher than 93%.