The new tridentate thioether ligands PhSi(CH2SMe)3 (1) and Ph-p-C6H4Si(CH2SMe)3 (2) have been synthesised and used for the preparation of the chelates fac-[W(kappa3-1)(CO)3] and fac-[W(kappa3-2)(CO)3], which were characterised by single-crystal X-ray diffraction. 1 and 2 were used as tripodal adsorbate molecules for the fabrication of self-assembled monolayers (SAMs) on gold. Film formation from solution was investigated in situ by second harmonic generation (SHG) and ellipsometry, which revealed a two-stepped process (fast adsorption, followed by slow film ordering). SAMs of 2 on gold were further investigated by ex situ methods, viz. high-resolution X-ray photoelectron spectroscopy (HRXPS), Fourier transform infrared reflection absorption spectroscopy (FTIRRAS), and scanning tunneling microscopy (STM). The latter two methods indicated dense packing of the tripodal anchor groups on the surface, with a substantially lower density of the biphenyl pricks. HRXPS showed three different binding states of sulfur, including a standard thiolate-type and a coordination-type state.