High molecular weight poly(p-phenylenebenzobisoxazole) (PBO) was prepared from poly(terephthalic acid anhydride) (PTAA) and 1,3-diamino-4,6-dihydroxybenzene dihydrogen-chloride in polyphosphoric acid (PPA). PTAA may react directly with the o-aminophenol groups to form benzoxazoles or react with PPA to generate terephthalic acid (TA) of very small particle size, which dissolves readily in PPA. PTAA provides the advantages of bypassing the requirement of small particle size TA, reducing the amount of water liberated by half, and possibly providing faster kinetics in PBO synthesis.