The study reported herein describes multifunctional effect of layered double hydroxide (LDH) modified with phosphonium-based ionic liquids (IL) containing phosphinate, carboxylate and phosphate anions on progress of ring-opening polymerization of epsilon-caprolactone under microwave irradiation. The extent of IL-modification had a crucial effect on the exfoliation of LDH. The non-modified LDH was able to catalyse the ring-opening polymerization of epsilon-caprolactone with polymer yield 89% but provided only micro composite material. On the contrary, LDH with intercalated IL-anions promoted exfoliation of LDH after only 3 min of microwave irradiation. The developed process is fast, environmentally-friendly (solvent-free) and adaptable to various polymer matrices, since a broad variety of IL-anions might be applied. (C) 2016 Elsevier Ltd. All rights reserved.