A complex of lithium tetrafluoroborate (LiBF4) and N-methylacetamide was prepared and investigated. Both LiBF4 and N-methylacetamide are solid at room temperature, but their mixture has liquid- or solid phase at room temperature, depending on the composition. When the complex is liquid, the complex has ionic conductivity. But if the complex is solid, it has electric conductivity. The room temperature ionic conductivities of some compositions in propylene carbonate of the complex exceed 6mS/cm. Room temperature electric conductivity of the complex is 5.025×10-3 mS/cm2. In addition, supercapacitors were constructed and tested using the above-mentioned complex electrolyte. The electrochemical properties of the complex and the supercapacitors were evaluated with cyclic voltammetry, ac impedance spectroscopy, etc. The supercapacitors with this complex show good electrochemical properties in specific capacitance, cycling performances.