Lower critical solution behavior in binary blends of hydrophobic polyethers with 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ahmim][Tf2N]) exhibited a difference in lower critical solution temperature (LCST) greater than 80 degrees C between structurally homologous poly(isopropyl glycidyl ether) (PiPGE) and poly(n-butyl glycidyl ether) (PnBGE). Replacement of the acidic hydrogen on the imidazolium ring with a methyl group (i.e., 2,3-dimethyl-1-hexyl-imidazolium bis(trifluoromethylsulfonyl)imide ([hmmim] [Tf2N])) significantly reduced the LCST of both the PnBGE/ionic liquid (IL) mixture and the PiPGE/IL mixture. Differing degrees of hydrogen bonding between the polymer and the cation cannot alone explain the observed behavior. Similar hydrogen bonding between the [hmim](+ )cation and both polymers from molecular dynamics simulations was consistent with this conclusion. However, stronger [hmim](+) cation tail/polymer alkyl side-chain interactions for PnBGE, with consequently stronger cation/anion interactions, point to solvophobic interactions as the basis for the large LCST difference between the PnBGE/[hmim][Tf2N] and PiPGE/[hmim][Tf2N] blends.