A new polymerization technique based on the use of sputtered metal particles for the thermal ring-opening polymerization of 1,1,3,3-tetraphenyl-1,3-disilacyclobutane (TPDC) was developed. This method facilitates the synthesis of polydiphenylsilylenemethylene (PDPhSM) thin films which are difficult to make by conventional methods because of their insolubility and high melting point. TPDC was first evaporated on silicon substrates and then exposed to metal particle deposition by sputtering prior to heat treatment. The catalytic activities of Pt, Pt/Pd, Au, Cu, and Ag particles were examined. The chemical structure of the film was basically the same, whatever the kind of metal used. However, the polymerization efficiency and film crystallinity depended greatly on the kind of metal under the same sputtering and heating conditions. The parts of the initial TPDC films that were not subjected to metal sputtering were entirely evaporated from the films without any polymerization. This phenomenon allowed us to make small polymer patterns. This method was also applicable to the ring-opening polymerization of hexaphenylcyclotrisiloxane.