This paper presents the first functionalization of silicon surfaces with well-defined, covalently attached monolayers containing saccharides. Two methods were used to this aim: a thermal method (refluxing in mesitylene) and a recently developed, extremely mild photochemical method (irradiation with 447 nm at room temperature). The results were analyzed by FT-IR and angle-resolved X-ray photoelectron spectroscopy. The use of a two-dimensional detector in ARXPS allows for unparalleled, subnanometer resolution in the determination of the elemental composition of monolayers. Even for monolayers with a total thickness of only approximately 1.5 nm, a clear elemental depth profile can be obtained. Such analyses display for sialic acid-containing monolayers that the mild photochemical attachment does not destroy the (rather fragile) sialic acid moiety and that the sugar is present at the top of the monolayer and thus available for biological interactions.