Thin, oriented films of poly-1,4-phenylene (PPP) were prepared with a specially designed reaction vessel. Various kinds of metals were deposited by vacuum evaporation on the PPP substrate, the temperature of which was able to be changed up to 400 °C. Of the studied metals, tellurium and bismuth exhibited the oriented crystallization on it. The oriented overgrowth of tellurium crystallites occurred in the temperature range of 150 °C–200 °C. There were two modes of oriented overgrowths of crystallites in the case of bismuth; one was performed by deposition around room temperature and the other at about 100 °C. The oriented overgrowths of bismuth and tellurium on PPP were examined in terms of the mismatch parameter of the crystal lattice, and it was found that the overgrowths were caused by the lattice matching at the interface between the crystallites of the metals and the PPP substrate.