Nitrogen-doped porous carbon nanofiber webs-sulfur composites (N-CNFWs/S) were synthesized for the first time with sulfur (S) encapsulated into nitrogen-doped porous carbon nanofiber webs (N-CNFWs) via a modified oxidative template route, carbonization-activation and thermal treatment. The composites were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET), X-ray powder diffraction (XRD), and thermogravimetry (TG) measurements. The results show that sulfur is well dispersed and immobilized homogeneously in the micropores of nitrogen-doped porous carbon nanofiber webs (N-CNFWs) with high electrical conductivity, surface area and large pore volume. The electrochemical tests show that the N-CNFWs/S composites with 60 wt. % of S have a high initial discharge capacity of 1564 mA h g(-1), a good cycling stability at the current density of 175 mA g(-1), and excellent rate capability (reversible discharging capacity of above 400 mA h g(-1) at 1600 mA g(-1)). (C) 2013 Elsevier Ltd. All rights reserved.