This study concerned a novel super-molecular ionic liquid synthesized by ammonium thiocyanate and caprolactam. The physical characters such as melting point and electric conductivity were investigated. Results showed that the melting point is -12.2°C at the molar ratio of 3:1 (caprolactam/ammonium thiocyanate), which is much lower than raw materials. The electric conductivities of synthesized ionic liquids were close to that of imidazole ILs. The structure of ionic liquid was characterized by IR, 1HNMR and quantum chemical calculations. It was shown that the NH4+ cation connected with caprolactam organic molecules by hydrogen bonds, leading to the forming of a super-molecular ion. The electrostatic attraction of super-molecular ion with anion was decreased because of the larger volume of super-molecular ion than original cation, thus the melting point decreased. The key properties that distinguish super-molecular ionic liquid from other ILs were the presence of supermolecular ion, which can be used to build up a hydrogen-bonded network. This type ion liquid was named as super-molecular ion liquid.