Sugammadex (SUG) is a synthetically modified γ-cyclodextrin derivative used in hospitals after surgeries to reverse the neuromuscular blockade induced by rocuronium or vecuronium. In this study, we aimed to develop the first electroanalytical quantification method for sugammadex by using molecular imprinting (MIP) via the electropolymerization (EP) technique. An EP-MIP film was formed by EP on a screen-printed gold electrode (SPAuE) and a new electrochemical sensor, EP-MIP(SUG)/SPAuE, was fabricated using the 4-aminophenol monomer with copper ions to enhance the MIP-binding site. Surface and electrochemical characterization of the EP-MIP(SUG)/SPAuE sensor have been done via scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). After screening and optimization studies were carried out to fabricate a MIP-based electrochemical sensor, the analytical performance of EP-MIP(SUG)/SPAuE and the validation parameters were tested according to the ICH guidelines. The specificity/selectivity of the developed sensor has been shown by using common interferents found in the biological fluids and also molecules having similar structures, such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. As a result, a quantitative analysis method has been developed and validated by using the EP-MIP(SUG)/SPAuE sensor in the concentration range of 0.1-1.0 pM with very high sensitivity (limit of detection: 27.3 fM). The applicability of the method has been shown for bulk drug substances, pharmaceutical dosage forms, and commercial serum samples with good recovery and RSD% results. The EP-MIP(SUG)/SPAuE is the first electrochemical sensor developed for the determination of sugammadex serving the aims of simplicity, short analysis time, and low cost, and has the potential to be adapted in the future as a portable and/or wearable sensor via miniaturization.