Synthesis of Cu2S dendritic nanostructures by a gas-solid reaction method has been achieved. The Cu2S dendritic nanostructure consists of a backbone and small branches aligning symmetrically and densely on the backbone like a double comb. Transmission electron microscopy has revealed that the backbone is along the c axis of monoclinic Cu2S and branches are along the b axis. Preoxidation of copper substrate is found to be important for high yield synthesis of the dendritic nanostructures. An oxide-assisted growth model is proposed to explain the formation of the dendritic nanostructures. Good field emission characteristics are also obtained from films of the dendritic Cu2S nanostructures.