Gas-phase synthesized multidecker V-2(benzene)(3) sandwich complexes were soft-landed onto a self-assembled monolayer of an n-octadecanethiol (C-18-SAM). The infrared absorption spectrum of this complex supported on the C-18-SAM was obtained by infrared reflection absorption spectroscopy (IRAS). The vibrational assignment of the IRAS spectrum for the V-2(benzene)(3) sandwich was based on a harmonic frequency analysis that employed density functional theory. The close similarity between the experimental and calculated results for the IR absorption frequencies demonstrates that the V-2(benzene)(3) complexes have a multidecker sandwich structure on the SAM substrate. Moreover, our thermal desorption study established that the sandwich complexes can be isolated on the SAM substrate up to a high temperature of similar to 350 K.