This paper reports the synthesis of alkanethiolate-functionalized core/shell Fe 3 O 4 /Au nanoparticles (Fe 3 O 4 @Au NPs) that combine the advantages of core/shell magnetic nanoparticles with self-assembled monolayers (SAMs). The alkanethiolates, having carboxylic acid (COOH) and methyl (CH 3 ) terminal groups, can be easily self-assembled on the Fe 3 O 4 @Au NPs substrates. The surface composition and structure of 11-mercaptoundecanoic acid (11-MUA) and 1-dodecanethiol (11-DDT) SAMs were characterized in detail using energy-dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS). To further study the surface properties of the SAMs, hydrophobic, ionic, and nonionic organic compounds were selected as probe molecules. The results indicated that the hydrophobic interaction caused strong retention of analytes, whereas the repulsive electrostatic interaction between the negatively charged 11-MUA SAMs surface and the negatively charged probe molecule would lead to the decrease of adsorption affinity.In the past few years, nanocomposite materials have been subjected to extensive research as the combination of different nanoscale functionalities are capable of endowing the substrate with enhanced properties and thus have great application potentials in various fields. [1][2][3][4][5][6][7][8][9][10][11] The core/shell nanostructure is an ideal composite system that combines the advantages of "core" and "shell" and has shown enhanced physical and chemical properties.The shell layer not only protects the core from oxidation but also provides a platform for surface modification and functionalization. Generally, magnetic materials are the most commonly selected substrates because they can readily be isolated from sample solutions by the application of an external magnetic field. However, magnetic particles suffer from several inherent limitations as they are likely to aggregate and lose magnetic properties when applied in complex environmental and biological systems. 11 Up to now, most of the research works focus on the preparation of Fe 3 O 4 @Au magnetite nanoparticles and there are only a limited number of literatures about its surface modification capabilities and its practical application. 13,14 Self-assembled monolayers (SAMs) of alkanethiolates on gold surfaces have been extensively studied and widely applied in