Improved reaction conditions for the preparation of poly(p-phenylene sulfide) (PPS) directly from bis(4-bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 C was obtained From BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc-BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1-chloronaphthalene and have properties comparable to commercial PPS. (c) 2005 Wiley Periodicals, Inc.