Modification of cytochrome c (cyt.c) by poly(ethylene oxide) (PEO) chains enabled the protein soluble in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquid without denaturation. However, as the solution was full of ions, suitable supporting electrolyte (KCl) was essential for the electron transfer reaction of cyt.c in the ionic liquid to attain adequate ion size for the active center.