NaTi2(PO4)3/C porous plates have been successfully synthesized via solvothermal approach with ammonia as inductive agent combined in-situ carbon coating. It reveals that the inductive agent plays a critical role in morphology-controllable fabrication. The morphology, structure, and electrochemical properties of NaTi2(PO4)3/C composites with multilayered plates, single-layered plate, porous multilayered plates all have been investigated, which are prepared by using urea, triethylamine, and ammonia, respectively. Among these samples, NaTi2(PO4)3/C porous multilayered plates with ammonia addition exhibit the best electrochemical properties due to their unique mesoporous structure. NaTi2(PO4)3/C porous multilayered plates deliver an initial specific capacity of 125 and 110 mAh g−1 at 0.1 and 1 C, respectively. Furthermore, NaTi2(PO4)3/C porous multilayered plates show a good rate capability, whose capacity and corresponding capacity retention reach 85 mAh g−1 and 82.4%, respectively, after 120 cycles under the high rate of 10 C. The excellent results indicate that the NaTi2(PO4)3/C porous multilayered plates are a promising electrode candidate for sodium ion battery.