Self-assembled monolayers (SAMs) on gold surfaces based on three kinds of acetylthio-surfactant-encapsulated polyoxometalate clusters (thio-SECs) terminated with multiple CH3COS- groups, (NC26H55S(CO)CH3)(6)H-2[Co(H2O)CoW11O39], (NC26H55S(CO)CH3)(13)H-3[Co-4(H2O)(2)(P2W15O56)(2)], and (NC26H55S(CO)CH3)(13)[Fe-4(H2O)(2)(P2W15O56)(2)]Br, have been prepared, which is representative of a general methodology to fabricate polyoxometalate-based SAMs. Thio-SECs self-assembled into monolayers on gold surfaces through the hydrolysis of CH3COS- groups and the subsequent formation of S-Au bonds, which was confirmed by grazing angle infrared spectroscopy, X-ray photoelectron spectroscopy, and ellipsometric and scanning tunneling microscopy (STM) measurements. Furthermore, the SAMs of the thio-SECs possess closely packed structures, and the local short-range order is clearly observed in the magnified STM image. We have also investigated the electrochemical behavior of SAMs of thio-SECs by cyclic voltammetry in detail, and the redox potential of the original polyoxometalates has been well retained. The electrochemical signals of the SAMs are very weak because of the small moiety of thio-SECs that are electrochemically accessible in the cyclic voltammetry experiments. The polyoxometalate-modified electrodes that we prepared are not only highly ordered in the local short range but also stable in electrochemical cycling because of the multiple S-Au bonds of thio-SECs on the gold substrates that aid in the construction of functional materials such as electrochemical and electrocatalytic devices.