Study　on　nanomaterials　has　attracted　great　interests　in　recent　years.　In　this　article,　zirconia　nanocrystallites　of　different　structures　have　been　successfully　synthesized　via　hydrothermal　methods　with　cationic　surfactant　(CTAB)　and　anionic　surfactant　(SDS),　respectively.　Differential　Scanning　Calorimeter　(DSC-TG),　X-ray　Diffractometer　(XRD),　Transmission　Electron　Microscope　(TEM),　Ultraviolet-Visible　(UV-vis)　and　N2　adsorption-desorption　analyses　are　used　for　their　structure　characteristics.　The　results　show　that　the　cationic　surfactant　has　a　distinctive　direction　effect　on　the　formation　of　zirconia　nanocrystallites,　while　the　anionic　surfactant　has　a　self-assembly　synergistic　effect　on　them.　The　sample　synthesized　with　the　cationic　surfactant　presents　good　dispersion　with　the　main　phase　of　tetragonal　zirconia,　and　the　average　nanocrystal　size　is　around　15　nm　after　calcination　at　500°C.　While　the　sample　synthesized　with　the　anionic　surfactant　exhibits　a　worm-like　mesoporous　structure　with　pure　tetragonal　phase　after　calcination　at　500°C　and　with　good　thermal　stability.