The conformational landscapes of two commonly used ionic liquid ions, the anion bis(trifluoromethanesulfonyl)amide (Ntf(2)) and the cations N-propyl- and N-butyl-N-methylpyrrolidinium, were investigated using data obtained from Raman spectroscopy, molecular dynamics, and ab initio techniques. In the case of Ntf2, the plotting of three-dimensional potential energy surfaces (PES) and the corresponding molecular dynamics (MD) simulations confirmed the existence of two stable isomers (each existing as a pair of enantiomers) and evidenced the nature of the anion as a flexible, albeit hindered, molecule capable of interconversion between conformers in the liquid state, a result confirmed by the Raman data. In the case of the N,N-dialkylpyrrolidinium cations, the PES show a much more limited conformational behavior of the pyrrolidinium ring (pseudorotation). Nevertheless, such pseudorotation produces two stable isomers with the propyl and butyl side chains in completely different positions (axial-envelope and equatorial-envelope conformations). This result was also confirmed by Raman spectra analyses and MD simulations in the liquid phase. The implications of the conformational behavior of the two types of ions are discussed in terms of the solvation properties of the corresponding ionic liquids.