As an important metal oxide, anatase titanium dioxide has been widely investigated because of its many promising properties for catalysis and photocatalysis. The properties of anatase TiO2 crystals are largely determined by external surfaces exposed. Many efforts have been made to improve the percentage of high-reactive facets like {001} facets of anatase TiO2 to enhance its catalytic properties. This review reports the recent progress in designing and fabricating high-reactive facets dominated anatase TiO2via various strategies including traditional vapor phase epitaxial processes, hydrothermal/solvothermal methods, nonhydrolytic alcoholysis methods and high temperature gas phase reactions. Furthermore, focusing on the (001) surface, the article also covers advances in the theoretic simulations of various high-reactive facets of anatase TiO2 crystals. Finally, we offer a summary and some perspectives on the challenges and new directions for future research in this emerging frontier.