Room temperature ionic liquids can affect the cis/trans state of peptide bonds. Cis/trans isomerization of proline-containing dipeptides is studied in 4 solvents. [C4mpy][Tf2N] leads to large cis/trans isomerization barriers in Xaa-Pro dipeptides. Cis state of Trp-Pro is found to be the preferred conformation in [C4mpy][Tf2N]. Ramachandran space explored is less in IL than other studied solvents.