Unique　ordered　TiO2　superstructures　with　tunable　morphology　and　crystalline　phase　were　successfully　prepared　by　the　use　of　different　counterions.　Dumbbell-shaped　rutile　TiO2　and　nanorod-like　rutile　mesocrystals　constructed　from　ultrathin　nanowires,　and　quasi-octahedral　anatase　TiO2　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　TiO2　superstructures　with　different　morphologies　and　crystalline　phases　are　also　proposed　based　on　a　series　of　experimental　results.　The　obtained　TiO2　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　TiO2　superstructures,　which　have　a　single-crystal-like　and　porous　nature.　Shape　of　things　to　come:　Unique　ordered　TiO2　superstructures　with　tunable　morphology　and　crystalline　phase　were　successfully　fabricated　by　the　use　of　different　counterions.　The　cells　made　of　TiO2　superstructures　exhibited　larger　capacity　and　improved　rate　performance　for　lithium　ion　intercalation.　Copyright　©　2012　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.