The synthesis of a new hydrophilic ammonium-based poly(ethylene glycol)-ionic liquid (PEG-IL) is reported; the structure was assigned by NMR (¹H, ¹³C) and MALDI mass spectrometry. The viscosity and thermal stability were also studied, as well as its polarity. Its application as an alternative solvent in the synthesis of dipeptides under microwave irradiation is also described.