In this study, gold electrodes (GE) modified with three kinds of thiolated calix[4,6,8]arenes (TCnA: TC4A, TC6A, TC8A) were successfully prepared using a simple self-assembly strategy. Three self-assembled films were characterized by cyclic voltammetry measurement, electrochemical impedance spectroscopy, static contact angle measurement and atomic force microscopy. The results confirmed that TCnA molecules effectively absorbed onto the surface of gold electrodes to fabricate the multilayer self-assembled films. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurement showed that the TCnA/GE exhibited high supramolecular recognition and enrichment capability and consequently displayed good electrochemical response toward dopamine (DA). Especially, TC8A/GE exhibited an excellent electrochemical performance for DA with high current densities of 1.5 mA mmol(-1) L cm(-2), broad linear range (1 x 10(-6) to 1 x 10(-3) mol L-1) and low detection limit (5 x 10(-7) mol L-1). The mechanism of supramolecular recognition and enrichment capability of TCnA/GE was discussed. (C) 2014 Elsevier Ltd. All rights reserved.