In this article we investigated the effect of solvents (CCl(4), CH(3)CN, DMF, ethanol, ethanol-H(2)O and H(2)O) on self-assembly of Thioctic acid (TA) and Mercaptohexanol (MCH) on gold by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Electrochemical characteristics of TA and MCH self-assembled monolayers (SAMs) formed in different solvents were evaluated by inspecting the ions permeability (interfacial capacitance C and phase angle Phi(1) (Hz)) and electron transfer capability (current density difference Delta i and charge transfer resistance R(ct)). Experimental results indicated that the ability of solvents availing the ordering of SAMs was: for TA, CCl(4)>ethanol>CH(3)CN>ethanol-H(2)O>DMF; for MCH, H(2)O>ethanol-H(2)O approximate to CCl(4)>ethanol approximate to CH(3)CN>DMF. Through relating the C, Phi(1 Hz), Delta i and R(ct) of SAMs (TA and MCH) with parameters of solvent (polarity E(T)(N), solubility parameter delta and octanol/water partition coefficients logP(ow)), it was found that solvents with bigger logP(ow) (smaller E(T)(N) and delta) availed the ordering of TA-SAMs but the effect of solvents on MCH self-assembly was complex and MCH-SAMs formed in H(2)O (the biggest a 6 and the smallest logP(ow)) and CCl(4) (the smallest E(T)(N), delta and the biggest logP(ow)) were more ordered than in other solvents. (C) 2011 Elsevier B.V. All rights reserved.