The graphene coated NaTi2(PO4)3 was prepared by a simple sol-gel method followed by calcination. The electrochemical properties of the NaTi2(PO4)3/graphene composite was firstly studied in detail when used as cathode electrode material for lithium-ion batteries. The electrochemical reaction mechanism of NaTi2(PO4)3/graphene composite was investigated by ex situ XRD.