Adrenaline and dopamine are very important catecholamine neurotransmitters in the mammalian central nervous system. Catecholamine drugs are also used to treat hypertension, bronchial asthma and organic heart disease, and are used in cardiac surgery and myocardial infraction. [1][2][3][4] The determination of catecholamines and their metabolites in body fluids, such as urine, plasma and serum, is one of the most important ways to evaluate the activity of the sympathetic nervous system and support the diagnosis of many diseases in fields of clinical medicine. Several highperformance liquid chromatography (HPLC) methods with online purification have been described for use in the analysis of catecholamines in biological samples using either fluorescence detection, [5][6][7] on-line chemical derivatization followed by fluorescence detection, [8][9][10][11] capillary electrophoresis 12,13 or flow injection analysis. 14,15 These methods generally have good sensitivity and reproducibility, and can meet practical requirements, but require expensive instruments, a well-controlled experimental condition and profound sample making. Therefore, simple methods are expected and attention has been paid to them. Electrochemical detection offers several advantages, including remarkable sensitivity, inherent minituralization and portability, independence of the optical path length or sample turbidity, low cost, low power requirements and high compatibility with advanced micromachining technologies. Because of the simple procedure and high sensitivity of electroanalysis and the electroactivity of catecholamines, studying and measuring catecholamines with electrochemical methods were carried out. HPLC coupled with electrochemical detection has been used for simultaneously measuring catecholamines. [16][17][18] In most of these applications, the use of bare electrodes for the electrochemical detection of catecholamines has a number of limitations, such as low sensitivity and reproducibility, a slow electron-transfer reaction, low stability over a wide range of solution composition and a high overpotential, at which the electron transfer process occurs. In order to maintain the stability of the electrode responses and also to improve the analytical characteristics of the detection of substrates, a chemical modification or electrochemical pretreatments should be applied to the working electrode.Gold electrodes modified with a self-assembled monolayer of 3-mercaptopropionic acid, 19 a glassy carbon electrode modified with cobalt(II) hexacyanoferrate films, 20 a glassy carbon electrodes modified with multiwall carbon nanotubes, 21 Pt and GC electrode modified with electropolymerization of luminal, 22 a L-cysteine self-assembled monolayer modified gold electrode, 23 a glassy carbon electrode modified with C60-dimethyl(β-cyclodextrine)2, 24 and a polyisonicotinic acid modified glassy carbon electrode, 25 have been used for the determination of catecholamines. Unfortunately, most modified electrodes used for catecholamines detection have cer...