Nanoporous anatase TiO2 mesocrystals with tunable architectures and crystalline phases were successfully fabricated in the presence of the butyl oleate and oleylamine. Especially, the introduced surfactants served as a carbon source, bring a uniform carbon layer (about 2–8 nm) for heightening the electronic conductivity. The carbon coated TiO2 mesocrystals assembled from crystalline tiny subunits have more space sites for sodium-ion storage. When the material was applied as an electrode material in rechargeable sodium-ion batteries, it exhibited a superior capacity of about 90 mA h g−1 at 20 C (1 C = 168 mA g−1) and a highly reversible capacity for 5000 cycles, which is the longest cycle life reported for sodium storage in TiO2 electrodes.