Near edge X-ray absorption fine structure spectroscopy was used to study the orientation of the alkyl chains in monolayers of (R3RN+)-R-1-N-2 and (R2R2N+)-R-1-N-2 (R-1 = methyl and R-2 = octadecyl), self-assembled on muscovite mica via ion exchange. The alkyl chains adopt a random orientation in the monooctadecylammonium ions. Dimethyldioctadecylammonium ions, however, form a well-ordered self-assembled monolayer, The average tilt angle between the alkyl chains and the surface normal is 38 degrees, The difference between the mono- and the dioctadecylammonium ions reflects at least partially the packing density of the alkyl chains. When adsorbed on muscovite mica, dimethyldioctadecylammonium ions establish monolayers that are similarly well ordered as alkanethiol monolayers on gold.