Temperature-responsive polymers (TRPs) with a phase transition temperature close to human physiological body temperature have attracted much attention in biomedical and pharmaceutical fields. Addition of small amount of cosolvent to TRPs is expected to influence the molecular interactions, thereby affecting the phase transition temperature of TRPs. Hence, it is possible to tune the phase behavior of TRPs and also drive transitions in TRPs by variation of chemical structure of cosolvent. To elucidate the conformational changes of the phase transition of TRP aqueous solution in ionic liquids (ILs), poly(N-vinylcaprolactam) (PVCL), a well known TRP was synthesized by solution polymerization. The lower critical solution temperature (LCST) behavior of polymer aqueous solution, with the addition of imidazolium-based ILs possessing same Cl- anion and a set of cations [Cnmim]+ such as 1-ethyl-3-methylimidazolium ([Emim]+), 1-butyl-3-methylimidazolium ([Bmim]+), 1-hexyl-3-methylimidazolium ([Hmim]+), 1-decyl-3-methylimidazolium ([Dmim]+), 1-allyl-3-methylimidazolium ([Amim]+) and 1-benzyl-3-methylimidazolium ([Bzmim]+), was monitored by using various sophisticated experimental techniques. The modulations on the LCST of PVCL aqueous solutions follow the order of [Emim][Cl]<[Amim][Cl]<[Bmim][Cl]<[Hmim][Cl]<[Bzmim][Cl]<[Dmim][Cl]. This order shows that the LCST value increase with increasing the alkyl chain length of cation from [Emim]+ to [Dmim]+ of IL. To the best of our knowledge, this is the first report on comprehensive unequivocal evidence of the phase transition behavior of PVCL in presence of imidazolium-based ILs. Copyright © 2017 Elsevier Inc. All rights reserved.