Monodisperse carbon hollow spheres encapsulating silver nanoparticles have been successfully synthesized by a facile approach with imidazolium ionic liquid ([C 14 mim]BF 4 ) as the soft template. Meanwhile, a novel Ag/C nanocomposite with an interesting structure, in which the carbon hollow spheres encapsulating silver nanoparticles were assembled by fine carbon wires, exists in this experiment. The Ag/C nanocomposites was characterized by XRD, TEM (HRTEM), SEM, FTIR spectroscopy, Raman spectrometer and energy dispersive X-ray analysis (EDX). The possible formation mechanism of the nanocomposites has been proposed.