We have synthesised novel ionic liquids (ILs) to show both cellulose dissolution ability and LCST-type phase transition after mixing with water. To realise both polar and hydrophobic properties, tetraalkylphosphonium cations and a series of carboxylate anions were employed to assume hydrophobic and highly polar properties, respectively. Effects of their alkyl chain length on the water compatibility and cellulose solubility of the corresponding ILs were systematically examined. We succeeded in synthesising novel ILs which dissolve cellulose and separable with water at moderate temperature. Through the present study, we have clarified that not only polarity but also density of ILs is an important factor in designing the ILs for cellulose dissolution.