By the self-assembly monolayer (SAM) organization, three new podands belonging to silylpropanethiols have been tested as to their ability to form nanolayers protecting the noble metal surface (gold or silver) and to form complexes with monovalent metal cations on the metal surfaces. The stable self-assembled chemisorbed layers, providing protection to metal surface against electrooxidation and capable of blocking propylene carbonate (PC) electroreduction and Li electrodeposition were produced. Reflection-absorption infrared spectroscopy (RAIRS) indicated cleavage of the S-H bond upon adsorption of species 1-3 with the formation of S-Ag bonds on the metal surface. By cyclic voltammetry, it was found that the primary adsorbate formed on a Au electrode at E-ad (between -0.2 and -1.2 V vs. SCE) underwent reductive desorption at E < -1.3 V vs. SCE. The structures of 1-3 and their complexes with Na+ cations on the Ag surfaces were calculated and visualized by the AM1d semi-empirical method.