Controllable growth of anatase TiO2 crystals with exposed high reactive crystal facets has aroused great attention in the fields of science and technology due to their unique structure-dependent properties. Recently, much effort has been paid to synthesize anatase TiO2 crystals with exposed high reactive {001} facets. Herein, we review the recent progress in synthesizing {001} facets dominated anatase TiO2 crystals with different morphologies by various synthetic methods. Furthermore, our review is mainly focused on the formation/etching mechanisms of {001} facets dominated anatase TiO2 crystals based on our and other studies. The extensive application potentials of the anatase TiO2 crystals with exposed {001} facets have been summarized in this review such as photocatalysis, photoelectrocatalysis, solar energy conversion, lithium ion battery, and hydrogen generation. Based on the current studies, we give some perspectives on the research topic. We believe that this comprehensive review on anatase TiO2 crystals with high reactive {001} facets can further promote the relative research in this field.