The synthesis of poly(dihalophenylene oxide)s by thermal decomposition of Fe(II), Ce(III) and Ce(IV) phenolato complexes with pyridine as neutral ligands were achieved at different temperature ranges (140 degrees - 250 degrees C) with different time intervals (3 - 48 hr) via atom transfer rearrangement radical polymerization (ATRRP). The complexes were characterized by FTIR, DSC, UV-Visible, mass spectroscopy, magnetic susceptibility and elemental analyses. Structural analyses of polymers were performed by H-1 and C-13-NMR, FTIR spectroscopic analyses, T-g by DSC and the molecular weights by viscometrical method. H-1-NMR spectra of polymers are quite similar in pattern except the relative intensities of two main peaks, all having branched structures. The lowest percent conversion values were observed for polymers synthesized from Fe(III) complexes compared to Ce(III) and Ce(IV) complexes. The glass transition temperature of the polymers were quite high indicating they are rigid polymers (162 degrees to 187 degrees C).