A novel synthesis of poly(dibromophenylene oxide) (P), conducting polymer (CP), and/or crosslinked polymer (CLP), and/or radical ion polymers (RIP) was achieved simultaneously from sodium 2,4,6-tribromophenolate by microwave energy in a very short-time interval. The synthesized polymers were characterized via elemental analysis, FTIR, H-1 NMR and C-13 NMR, X-ray diffraction spectroscopy, SEM, DSC, TGA, ESR, GPC, conductivity measurement, and light scattering. It was found that polymerization proceeds through both 1,2- and 1,4-addition at equal rates. The effects of the energy and time on the % conversion and the polymer synthesis were investigated. The optimum condition for synthesis of P (the highest M-wr 2.97 x 10(5) g/mol) and CP was 70 W for 5 min in 5 ml, water and 100 W for 1 min in 0.5 mL water, having maximum values 23.6% and 27.2%, respectively. In addition, synthesis of CLP and RIP were achieved in 5 mL water at 350 W and 700 W at the end of 1 min, respectively. The direct synthesis of highly conducting polymer, with the conductivity of 1 S cm(-2) was achieved in the absence of applied doping process in a very short time sequence. P, CP, CLP, and RIP had fine granular, sponge-like, dendrite, and coarse surface structures, respectively. (c) 2006 Wiley Periodicals, Inc.