In order to obtain atomistic insights into the initial stages of the formation of the solid electrolyte interphase (SEI) in Na ion or Na metal batteries, we employ surface chemistry experiments and DFT calculations to study the interactions and reactions between a Na surface and the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMP-TFSI), a candidate to be used as electrolyte in batteries. Oxygen-free Na thin films, which were grown on Ru(0001) and characterized by X-ray and ultraviolet photoelectron spectroscopy (XPS, UPS), can be understood as model of a Na-rich electrode. After deposition of submonolayer to multilayer BMP-TFSI films on the Na thin films at room temperature, XPS measurements revealed partial decomposition and the formation of a ‘contact layer’ at the Na surface, consisting of mainly TFSI-based decomposition products.