A series of new dication imidazolium-based chiral ionic liquids were synthesized. Novel solid-liquid two-phase systems based on the chiral ionic liquids were developed. Excellent effect on enantiomeric separation of racemic phenylalanine was achieved with e.e. 99.2% and yield 85.2% for L-enantiomer in solid phase. The separation process is characteristic of no organic solvent, simple operation and fast separation process.