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The surface structure of trimethylpropylammonium bis(trifluoromethanesulfonyl)imide (TMPA TFSI) is studied by high-resolution Rutherford backscattering spectroscopy at room temperature. The results provide direct evidence of the molecular ordering at the surface. The C1conformer of the TFSI anion is dominant among two stable conformers, and the anions are oriented with their CF3groups pointing toward the vacuum in the outermost molecular layer. The anions in the second molecular layer also show preferred orientation although it is rather weak. [ABSTRACT FROM AUTHOR]