In this paper，the enrichment behavior of triclosan on multi-walled carbon nanotubes supported ferric hydroxide nanoparticles modified glassy carbon electrode was investigated by cyclic voltammetry with solid-phase microextraction.The extraction process was observed to follow the first-order kinetic equation based on Temkin isothermal adsorption model. The cyclic voltammogram of triclosan on the modified electrode showed an irreversible oxidation peak at about 0.558V.The linearity existed between the pH values and the oxidation peak potential indicated that the oxidation of triclosan was a transferred process of one electron accompanied by a proton. The oxidation peak current increased linearly with the increase of sweep rate，indicating that the oxidation reaction was controlled by surface adsorption. The linear relationship between the oxidation peak current and the logarithm of triclosan concentration in the range of 3.333×10-6-3.333×10-4mol/L could be used to determine the concentration of triclosan with the detection limit of 3.333×10-6mol/L.The method was used in detection of triclosan in hand sanitizers with good reproducibility and selectivity. Based on the cluster models of triclosan and ferric hydroxide nanoparticles，semi-empirical molecular orbital calculations were performed with PM7 in MOPAC2012.The thermodynamic and front orbit correlation coefficient results showed that a complex formed between triclosan and ferric ions was stable with the ΔG<0，and the electron transfer occurred in the formation of the triclosan complex.