The continuous copper films have been deposited on the surfaces of polyacrylonitrile fibers prepared by electrospinning process. Then the monoclinic-phase Cu2S thorny rods were obtained under the mixed gas of H2S and O-2 by using the copper-coated fibrous mats as substrate. The silver could be deposited conveniently on the surface of copper-coated fibrous mats by using sacrificial method. When the silver-gilt copper-coated fibrous mats were used as substrates and treated under the same atmosphere, the monoclinic-phase Cu2S4 with bottle- and thorny rod-shape could be obtained. The results revealed the fact that whether silver was present or not, the amount of the copper deposited on the fibrous mats could affect the component and morphology of the formed copper sulfide microstructure. The growing process of these special microstructures of copper sulfide was investigated and the possible mechanism was also suggested. (C) 2009 Elsevier B.V. All rights reserved.