A simultaneous synthesis of white poly(dibromophenylene oxide) (P) or yellow radical ion polymer (RIP) and black conducting polymer (CP) were achieved from potassium 2,4,6-tribromophenolate by microwave energy in a very short time. Polymerizations were carried out (i) under constant microwave energy and constant amount of water with different time intervals ranging from I to 7 min or (ii) at constant time intervals and constant amount of water with variation of microwave energy ranging from 70 to 900 watt or (iii) at constant time intervals and constant microwave energy with changing amount of water ranging from 0.5 to 5 mL. The synthesis of P and CP were achieved in 3 min at 70 watt and in I min in the range of 180-900 watt in 0.5 mL water whereas RIP was only achieved either at 70 or 350 watt in 17 or 25 min and in 0.5 or 5 mL water. The optimum conditions for synthesis of P, RIP and CP were for (i) 350 watt for 3 min in 5 mL water, for (ii) 350 watt for 25 min in 5 mL water and for (iii) 500 watt for I min in 0.5 mL water with maximum values of 39.2, 35.0 and 27.9%, respectively. RIP was synthesized only at 70 watt in 17 min and at 350 watt in 3 min, having maximum conversion value of 35.0%. The polymers were characterized via elemental analysis, FT-IR, (1)H and (13)C NMR, X-ray diffraction spectroscopy, DSC, TGA-FTIR, ESR, SEM conductivity measurement and Light Scattering. Polymerizations of P and RIP were proceeding though both 1,2- and 1,4-addition at equal rates having a branch structure and their molecular weights were 8.1 x 10(4) g/mol and 1.2 x 10(4) g/mol respectively. P and RIP were rigid polymers having high T(g) values. The synthesis of conducting polymer, with the conductivity of 1.34 S cm(-2) was achieved in the absence of doping process.