The simultaneous polymerization and formation of polyphenylacetylene film by Nd(P-204)(3)-Fe(AA)(3)-Al(i-Bu)(3) catalyst system have been investigated. The combined catalytic effects between rare earth phosphonates with M(T)(naph)(x) or Fe(AA)(3) systems are first proposed and compared. The polymerization features and kinetic behaviors with Nd(P-204)(3)-Fe(AA)(3)-Al(i-Bu)(3) system are described and discussed. The combined catalytic effects have the following order, respectively : Fe much greater than Co > Cr > Mn-Ni, Nd(P-204)(3)-Nd(P-507)(3) > Nd(P-350)(3), and Tb > Sm > Yb > Ho > Lu > Dy > Nd-Er-Pr > Y-Tm > Ce > Gd > La. The overall polymerization activation energy was found to be 20.8 kJ/mol showing coordination-anionic polymerization characteristic. PPA films so obtained are very similar to the rare earth ones.