We have developed a new method to fabricate poly(diphenylsilylenemethylene) (PDPhSM) matrix nanocomposite thin films containing copper nanoparticles produced by laser ablation in this paper. First of all, 1,1,3,3-tetra- phenyl-1,3-disilacyclobutane (TPDC) films were deposited on 4 cm2 silicon substrates cut from c-Si wafers by conventional vacuum evaporation under a pressure of 3.0×10-5 Torr; then copper nanoparticles were deposited onto the TPDC films by laser ablation; finally the TPDC films with copper nanoparticles were heated in an electric furnace in an air atmosphere at 553 K for 10 min to induce ring-opening polymerization of TPDC. The results indicated that it is possible to fabricate PDPhSM matrix nanocomposite thin films using copper nanoparticles produced by laser ablation. The morphology and size distribution of copper nanoparticles can be controlled by laser ablation conditions. Also, the polymerization efficiency depends on the size and chemical state of copper nanoparticles.