Direct incorporation of ionic liquid onto the upper rim of calix[4]resorcinarene led to the formation of tweezer-like calix[4]resorcinarene via one-pot strategy. The formation of this cationic supramolecular structure was confirmed by H-1 NMR, C-13 NMR, CHNS, TGA and DTA techniques. The hydrophobic central cavity and hydrophilic cationic arms render it a suitable heterogeneous phase transfer catalyst for the preparation of valuable azidohydrins in water. The recovered catalyst could be used for several times without any significant loss of activity.