With　the　aim　of　enhancing　the　electrochemical　kinetics　and　capacity　of　the　TiO2　electrode　for　Na　ion　batteries　(NIBs),　we　have　designed　a　hybrid　material　of　carbon-coated　TiO2　mesocrystals　anchored　on　reduced　graphene　oxide　(TiO2@C-rGO).　Such　hybrid　nanostructures　are　fabricated　through　a　facile　one-step　route　including　in　situ　growth　of　oriented　self-assembly　of　TiO2　mesocrystals　on　GO.　TiO2@C-rGO　possesses　a　very　large　surface　area　(279　m2　g-1),　mesoporous　nature,　and　single-crystal-like　structure.　It　is　also　found　that　the　capacity　of　TiO2　electrode　for　NIBs　could　be　improved　by　carbon　coating　at　a　low　current　rate,　but　pure　TiO2　shows　better　rate　performance　than　that　of　TiO2@C.　Remarkably,　the　enhanced　electrochemical　kinetics　and　large　capacity　can　be　simultaneously　achieved　by　designing　hybrid　material.　The　hybrid　nanostructures　exhibit　a　highly　reversible　capacity　of　300　mAh　g-1　at　100　mA　g-1,　superior　rate　capability,　and　long-term　cycling　stability　(a　stable　capacity　of　159　mAh　g-1　can　be　maintained　after　1000　cycles　at　1　A　g-1).　The　superior　Na　ion　storage　of　TiO2@C-rGO　is　largely　ascribed　to　the　robust　architecture　of　well-dispersed　carbon-coated　mesoporous　TiO2　mesocrystals　anchored　on　conductive　graphene　network,　leading　to　enhanced　electrochemical　kinetics　and　offering　enough　active　sites　for　the　Na　ion　to　locate.　©　2016　American　Chemical　Society.