Unique　ordered　TiO　2　superstructures　with　tunable　morphology　and　crystalline　phase　were　successfully　prepared　by　the　use　of　different　counterions.　Dumbbell-shaped　rutile　TiO　2　and　nanorod-like　rutile　mesocrystals　constructed　from　ultrathin　nanowires,　and　quasi-octahedral　anatase　TiO　2　mesocrystals　built　from　tiny　nanoparticle　subunits　were　achieved.　Interestingly,　the　obtained　anatase　mesocrystals　have　a　fine　microporous　structure　and　a　large　surface　area.　The　influence　of　the　counterions　in　the　reaction　system　is　discussed　and　possible　mechanisms　responsible　for　the　formation　of　the　unique　ordered　TiO　2　superstructures　with　different　morphologies　and　crystalline　phases　are　also　proposed　based　on　a　series　of　experimental　results.　The　obtained　TiO　2　superstructures　were　used　as　anode　materials　in　lithium　ion　batteries,　and　exhibited　higher　capacity　and　improved　rate　performance;　this　is　attributed　to　the　intrinsic　characteristics　of　the　mesoscopic　TiO　2　superstructures,　which　have　a　single-crystal-like　and　porous　nature.　Shape　of　things　to　come:　Unique　ordered　TiO　2　superstructures　with　tunable　morphology　and　crystalline　phase　were　successfully　fabricated　by　the　use　of　different　counterions.　The　cells　made　of　TiO　2　superstructures　exhibited　larger　capacity　and　improved　rate　performance　for　lithium　ion　intercalation.　Copyright　©　2012　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.