Eighteen aliphatic linear amines, from methylamine to stearylamine, have been experimentally studied by NMR and theoretically calculated at the GIAO/B3LYP/6-311++G(d,p) level. A partial exploration of their conformation has been carried out, mainly to determine the effect on the chemical shifts. In solution and for neutral amines, 15N chemical shifts indicate a mixture of two conformations. In the solid state (CPMAS NMR) only the subset of solid amines has been studied (from C14 to C18). The 15N signals of the corresponding ammonium salts in the solid state depend on the counteranions, Cl− and CF3CO2−, a result that is theoretically proven.