Deep eutectic solvents have obtained growing interest in analytical chemistry due to opportunities related the green chemistry paradigm, i.e., substitution of organic solvents, application of nontoxic ingredients and minimal quantities of wastes formed in their synthesis and usage. In this work, the advantages of deep eutectic solvents were shown in the development of electrochemical sensor for epinephrine determination. Polythionine molecularly imprinted with epinephrine (PTNMIP) was electrodeposited from natural deep eutectic solvent (NADES) consisted of citric acid, glucose, and water in 1:1:6 molar ratio and tested with standard solutions of epinephrine, pharmaceutical preparations, and artificial samples of biological liquids. Only one drop (100 µL) of the monomer dissolved in NADES was applied for sensor preparation on the platform of screen-printed carbon electrode. Electropolymerization was performed by multiple scanning of the potential. The formation of molecular imprints was confirmed by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). After the template removal, the charge transfer resistance of the surface layer depended on the epinephrine concentration in the range from 100 nM to 316 µM (limit of detection 50 nM). Selectivity of the signal was confirmed against serotonin and norepinephrine commonly present in biological liquids. Sensor was successfully tested for the determination of epinephrine in spiked solutions mimicking influence of the plasma electrolytes, serum proteins, and in real saliva samples. The recoveries calculated for 10 μM epinephrine ranged from 98.3 to 102.6%. Insignificant influence of the additives and stabilizers present in medications was eliminated by sample dilution. Impedimetric sensor developed showed good opportunities for further application in clinical diagnostics, pharmacokinetics studies and medication manufacture control.