To meet the requirements of the energy storage materials for high energy density and high power density, unique niobium carbide-derived carbon (NbC-CDC) coated graphitized mesophase carbon microbead (GMCMB) composites (GMCMB@NbC-CDC) with core-shell structure were prepared by chlorinating the precursor of graphitization mesophase carbon microbead@niobium carbide. The microstructure of NbC-CDC was characterized as mainly amorphous carbon combined with short and curved sheets of graphene, and the order degree of carbon layers increases with the chlorination temperature. The composites exhibited a tunable specific surface area and micropore volume, with micropore size of 0.6∼0.7nm. Compared with the pure GMCMB, the GMCMB@NbC-CDC composites manifested higher charge (726.9mAhg−1) and discharge capacities (458.9mAhg−1) at the first cycle, which was probably that Li ions could insert into not only carbon layers of GMCMB but also micropores of NbC-CDC. After 100 cycles, the discharge capacity of GMCMB@NbC-CDC chlorinated at 800°C still kept 384.6mAhg−1, which was much higher than that of the pure GMCMB (305.2mAhg−1). Furthermore, the GMCMB@NbC-CDC composites presented better rate performance at higher current densities.