Tetrazines were immobilized onto electrogenerated films of polypyrrole functionalized with beta-cyclodextrin. Their immobilization was ascribed to the formation of the inclusion complexes between the tetrazines derivatives and the beta-cyclodextrin cavity. We proved that the resulting supramolecular material kept the electrochemical and fluorescent properties of tetrazines. This original architecture was used with success as a "bridge" to immobilize the beta-cyclodextrin-tagged glucose oxidase, chosen as an enzyme model, to prove the efficiency of the method to build new supra-biomolecular architectures. (C) 2016 Elsevier B.V. All rights reserved.