Polymerization of 2,4,6-trichlorophenol (TCPH) was achieved through the thermal decomposition of the copper and cobalt complexes of TCPH with N-containing ligands [N-methyl imidazole (NMIz) and 3,5-dimethyl pyrazole (DMPz)]. The structural analysis of the complexes was performed by using Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), mass (MS), UV-VIS, diffuse reflectance (DRS) and electron spin resonance (ESR) spectroscopies, magnetic susceptibility balance and elemental analyses. Polymerization was achieved either in solid state or in melt, and the polymers were characterized by FTIR, nuclear magnetic resonance (NMR) spectroscopy, DSC, and viscosity measurements. The effects of the temperature and time dependencies of %Conversion on polymer synthesis were investigated. The cobalt complexes (having higher decomposition temperatures) were more stable than copper complexes (decomposing at lower temperatures). Thermal stability with respect to N-ligand shows that the complexes with NMIz are more stable than DMPz complexes of the same metal. The highest molecular weights (M w ) were achieved at the end of 3 hr of polymerization for C1 at 1708C, C2 at 1208C, and C4 at 1508C. The longer time at lowest conversion leads to highest M w of C1 at 1258C at the end of 24 hr, C2 at 908C at the end of 72 hr and at 1008C at the end of 48 hr.The M w of the polymeric products range between 8.5 Â 10 3 and 6.5 Â 10 4 . All polymers are rigid and have branched structures.