A facile approach was developed for synthesis of carbon hollow microspheres (CHM) via carbonization of the hollow polymer microspheres prepared from polymerization in the presence of l-lysine acted as in situ template. The physical and chemical structures of the samples were investigated by X-ray powder diffraction, Raman spectrum, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). SEM and TEM images show that the products consist of a large scale of monodisperse CHM with a size of about 1.1-1.3 mu m. Furthermore, the resulting CHMs possess a surface area of 559 m(2) g(-1) and a pore volume of 0.27 cm(3) g(-1). The morphology and the size of the as-obtained samples can be controlled by the polymerization temperature, polymerization time, and the dosage of l-lysine. Moreover, a possible formation mechanism of the CHM has been put forward according to the experimental data available.