A fluorescent calix[4]arene triazole-linked pyrene (CP) was carefully designed and synthesized via click chemistry. The modification of CP with graphene oxide (GO) by a simple non-covalent interaction strategy is presented. Further inspection by electrochemical impedance spectroscopy reveals that the CP-GO could exhibit a very high supramolecular recognition for carbaryl, in particular in serum samples with a nanomolar concentration detection. Additionally, it is easy to directly observe macroscopic recognition by the contact angle, and expand practical applications.