Porous anatase TiO2 single crystal architectures with large specific surface area and remarkable crystalline phase-stability were fabricated via a green microwave-assisted process. Ionic liquid was chosen as both an essential structure-directing agent for the formation of the {001} facets exposed TiO2 and an etching agent source for selective erosion of the exposed {001} facets, leading to robust porous framework with exposed {101} facets. These porous anatase single crystals were thermally stable up to 800 degrees C, indicating excellent structure stability. The product showed stable cyclability at high current rate, better reversibility, and high Coulumbic efficiency of 100% for lithium storage.