In this paper, we demonstrate the design and synthesis of novel mesoporous Si@C microspheres as anode materials for high-performance lithium-ion batteries. SiO2 nanoparticles modified with hexadecyl trimethyl ammonium bromide are enveloped within resorcinol-formaldehyde polymer microspheres which form in the ethanol-water-ammonia system. Mesoporous voids between Si nanoparticles and the carbon framework are generated after carbonization at 800 °C and magnesiothermic reduction at 650 °C. The resultant Si@C microspheres show regular spherical shapes with a mean diameter of about 500 nm, a mesopore size of 3.2 nm and specific surface areas of 401-424 m(2) g(-1). Mesoporosity of Si@C microspheres effectively buffers the volume expansion/shrinkage of Si nanoparticles during Li ion insertion/extraction, which endows mesoporous Si@C microspheres with excellent electrochemical performance and cycle stability when they are used as lithium-ion battery anode materials. A typical sample of mesoporous Si@C microspheres presents a specific capacity of 1637 and 1375 mA h g(-1) at first discharge and charge under a current density of 50 mA g(-1). After 100 cycles, the charge capacity remains 1053 mA h g(-1) with a coulombic efficiency of 99%, showing good cycle stability of the anode. This finding highlights the potential application of mesoporous Si@C microspheres in lithium-ion battery anode materials.