Porous carbon nanotubes (CNTs) are obtained by removing MoO2 nanoparticles from MoO2@ C core@shell nanofibers which are synthesized by phase-segregation via a single-needle electrospinning method. The specific surface area of porous CNTs is 502.9 m(2) g(-1), and many oxygen-containing functional groups (C=OH, C=O) are present. As anodes for sodium-ion batteries, the porous CNT electrode displays excellent rate performance and cycling stability (110 mA h g(-1) after 1200 cycles at 5 A g(-1)). Those high properties can be attributed to the porous structure and surface modification to steadily store Na+ with high capacity. The work provides a facile and broadly applicable way to fabricate the porous CNTs and their composites for batteries, catalysts, and fuel cells.