Structural and morphological control is an effective approach for improvement of electrochemical properties in rechargeable batteries. One-dimensionally assembled ,structure composed of NASICON-type Na3V2(PO4)(3) nanoparticles were fabricated through an electrospinning method to meet the requirements for the development of efficient electrode materials in Na-ion batteries. High-temperature treatment of electrospun precursor fibers under an argon flow provides a nonwoven fabric of nanowires comprising crystallographically oriented nanoparticles of NASICON-type Na3V2(PO4)(3) within a carbon sheath. The mesostructure comprising NASICON-type Na3V2(PO4)(3) and carbon give a short sodium-ion transport pass and an efficient electron conduction pass. Electrochemical properties of NASICON-type Na3V2(PO4)(3) are improved on the basis of one-dimensional nanostructures designed in the present study.