We designed a series of novel carbamate-containing organometallic hyperbranched polymers, namely, generation 1 to generation 3 of ferrocene-terminated hyperbranched polyurethane (HBPU-Fc). We report here in full details on synthesis, characterization, and redox behaviors of HBPU-Fcs, which are expected to serve as supramolecular receptors for direct sensing glucose and Adenosine Triphosphate (ATP). The synthetic route involved the construction of the hyperbranched polymer fragments. The different redox behaviors of the new metallic hyperbranched polyurethane and its film immobilized on electrode were studied by cyclic voltammetry and differential pulse voltammetry (DPV). The application of HBPU-Fc in direct electrochemical sensing to glucose and ATP anion (Adenosine-5' Triphosphate, ATP(2-)) were carried out using HBPU-Fc as receptor. HBPU-Fc exhibited significant responses to both anion ATP(2-) and neutral molecule glucose. Some structural recognitions and supramolecular interaction of HBPU-Fc with glucose or with ATP(2-) changed the course of electron transfer in ferrocene/ferrocenium redox couple. This finding makes HBPU-Fc a promising candidate for biosensing material. (C) 2014 Elsevier B.V. All rights reserved.