In　this　study,　a　simple　hydrothermal　route　was　developed　for　the　synthesis　of　the　square-like　anatase　TiO2　nanocrystals　starting　from　TiOA　and　NH4F　raw　materials.　The　synthesized　nanocrystals　exhibited　a　high　percentage　64%　of　exposed　{0　0　1}　facets　and　highly　crystalline.　The　size　of　square-like　nanocrystals　was　found　to　be　ca.　50-80　nm　and　their　thickness　was　10-20　nm.　It　was　found　that　the　intermediate　TiOF2　QDs　formed　before　the　hydrothermal　reaction　played　a　key　role　for　the　formation　of　square-like　anatase　TiO2　nanocrystals.　Based　on　a　series　of　experimental　results,　a　possible　mechanism　for　the　formation　of　square-like　anatase　TiO2　nanocrystals　with　a　highly　exposed　{0　0　1}　facet　was　proposed.　©　2012　Elsevier　B.V.　All　rights　reserved.