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The determination of thyroid hormones has practical clinical significance for the diagnosis of hyperthyroidism and hypothyroidism diseases. Considering this aspect, a wide range of analytical methods for the detection of analytes, including immunoassay, chemiluminescence, mass spectroscopy and high-performance liquid chromatography, among others, has been developed. This type of analysis provides feasible results. Nevertheless, it requires qualified staff, special facilities and is time-consuming. For this reason, this paper relies on the fabrication of an electrochemical device developed with inkjet printing technology for the free detection of Thyroxine (T4). To manufacture our electrochemical device, several aspects were considered from the use of materials that amplify electrical signals, to finding a supramolecular scaffold that possess affinity towards the target analyte and the need of preconcentrating the analyte on the electrode's surface. For this task, printed devices were modified with a hybrid nanomaterial consisting of reduced graphene oxide (rGO) tuned with Au nanoparticles (Au–NPs) and an entrapment agent and different thiolated cyclodextrins (x–CD-SH) as carrying agents. Analytes were preconcentrated via supramolecular chemistry due to the formation of an inclusion complex between the cyclodextrin and hormones. Morphological and electrochemical characterization of the final device was carried out to ensure the proper workability of the electrode, achieving excellent response, sensitivity and limit of detection (LOD). [ABSTRACT FROM AUTHOR]