Atomic composition of monolayers based on siloxane dimer of quaterthiophene deposited by Langmuir–Blodgett technique on a silicon dioxide surface partially covered by gold film and the stability of these monolayers upon surface treatment by Ar⁺ ions bombardment have been studied. Experimental results for the chemical composition of a series of studied surfaces have been obtained by X-ray photoelectron spectroscopy (XPS) by recording XPS spectra of C 1s, O 1s, S 2p, and Au 4f core levels. The relative concentration of Au and Si substrate atoms and the composition of ex situ prepared surface under study were determined within 10–15%, which indicates that Langmuir–Blodgett monolayers based on siloxane dimer of quaterthiophene form continuous coating in a considerable extent. Prior to the treatment of the studied surface by Ar⁺ ions bombardment, carbon- and oxygen-containing surface adsorbates provided a considerable contribution to the results of XPS measurements. The surface cleaning by Ar⁺ ions with energy 3 keV at electric current through sample of ~1 μA in several 30-s steps has led to the etching of surface adsorbates and next Langmuir–Blodgett films of the siloxane dimer of quaterthiophene.