Hollow N-doped carbon/metal phosphate (HNC/MP) structure is prepared via the reaction of ZIF-8@ZIF-67 with NH4H2PO4, and ultra-small nanoparticles (metal phosphate, etc) are evenly embedded in amorphous carbon walls. Evaluating for a Li-S battery, HNC/MP composites with 62 wt% sulfur exhibits a large initial capacity of 921mAh g(-1) at 800mAg(-1), an impressive cyclability of 580mAh g(-1) after 200 cycles and good rate performance of 637.1mAh g(-1) at 1600mAg(-1), which are chalked up to phosphorization and hollow structure.