We report herein an effective strategy for recognizing of 2,4,6-trinitrotoluene (TNT) molecules at the surface of graphene polyaniline (PANI) nanocomposites. The imprinted template was synthesized using picric acid as a template analogue for the explosive. The recognition sites were generated by the extraction of the imprinting template from GN-PANI-molecularly imprinted polymer film. The morphology of preparing films was investigated using scanning electronic microscopy images. The differential pulse voltammograms and cyclic voltammograms were used for TNT detection. The results reported here could form the basis of a new strategy for preparing various polymercoating layers on PANI supports and the molecular imprinting techniques discussed could also find applications in the fields of separation and environmental monitoring.