This work presented the synthesis and characterization of new ionic liquid-coordinating ruthenium complexes. The resulting ruthenium complexes exhibited not only excellent thermoregulated phase-separation behavior but also highly catalytic activity and enantioselectivity for the asymmetric hydrogenation with molecular hydrogen. The thermoregulated ionic liquid catalyst was highly resistant to leaching and was recycled consecutively for six times without significant loss of catalytic activity and enantioselectivity. The presence of RuH species revealed that NH and a RuH unit, involved in the hydride transfer process, were of great importance in the present catalytic system.