We describe a preparation of sulfur-doped mesoporous amorphous carbon (SMAC) from a commercially available alkyl surfactant sulfonate anion-intercalated NiAl-layered double hydroxide precursor via thermal decomposition and subsequent acid leaching. The resultant amorphous carbon is endowed with the integrated advantage of featuring high reversible capacity and long cycling stability: intrinsic doping of sulfur, large specific area, and broad mesopore size distribution. Electrochemical evaluation shows that the SMAC electrode exhibits highly enhanced electrochemical performances, compared with the electrode of non-doped mesoporous and amorphous carbon prepared by using a different surfactant (sodium laurate). A high reversible capacity of 958mAhg−1 is achieved for the SMAC electrode after 110 cycles at 200mAg−1, and especially a superlong cycle life with a reversible capacity of 579mAhg−1 after 970 cycles at 500mAg−1. Moreover, the SMAC electrode can facilitate the reversible insertion/extraction of Na ion, owing to the proper specific area and mesopore size distribution, as well as the improved electronic conductivity resulted from doping of sulfur.