Nitrogen-doped mesoporous carbon hollow spheres (N-MCHS) have been synthesized by a one-pot and surfactant-free method, in which TPOS and resorcinol/formaldehyde as the silica and carbon precursor, respectively. Especially, ethylenediamine (EDA) as both the base catalyst for the co-condensation process between the in situ generated silica primary particles, the polymer oligomers, and the nitrogen precursor. They possessed uniform size of ~200nm, resultant N-MCHS shows excellent performance for the anode of lithium-ion batteries (LIBs) .