TiO₂ nanosheets with highly reactive {001} facets ({001}-TiO₂) have attracted great attention in the fields of science and technology because of their unique properties. In recent years, many efforts have been made to synthesize {001}-TiO₂ and to explore their applications in photocatalysis. In this review, we summarize the recent progress in preparing {001}-TiO₂ using different techniques such as hydrothermal, solvothermal, alcohothermal, chemical vapor deposition (CVD), and sol gel-based techniques. Furthermore, the enhanced efficiency of {001}-TiO₂ by modification of carbon materials, surface deposition of transition metals, and non-metal doping is reviewed. Then, the applications of {001}-TiO₂-based photocatalysts in the degradation of organic dyes, hydrogen evolution, carbon dioxide (CO₂) reduction, bacterial disinfection, and dye-sensitized solar cells are summarized. We believe this entire review on TiO₂ nanosheets with {001} facets can further inspire researchers in associated fields.