Necklace-like hollow carbon nanospheres (CNSs) have been successfully synthesized from the pentagon-including reactants, which provide an auxiliary example for the theoretical prediction that necklace-like hollow CNSs are assumed to be composed of the regular occurrence of nonhexagonal rings at the atomic level. Benefits of the as-obtained hollow CNSs also arise from the high Brunauer-Emmett-Teller value of 594.32 m(2)/g and a narrow pore distribution at 5 nm. The electrochemical hydrogen storage experiments for the as-obtained necklace-like hollow CNSs exhibit a capacity of 242 mAh/g at the current density of 200 mA/g, corresponding to a hydrogen storage of 0.89 wt%, which is higher than the previously reported electrochemical capacities for the multiwalled carbon nanotubes (MWCNTs). Furthermore, the as-obtained necklace-like hollow CNSs show a lithium capacity advantage compared with the carbon solid particles for application in lithium batteries. These results indicate that the necklace-like hollow CNSs provide a new candidate for the application in hydrogen storage and lithium batteries.