Polybenzoxazole (PBO) fibers with a submicron diameter were successfully prepared by electrospinning its precursor, polyhydroxyamide (PHA), solutions to obtain the PHA fibers first, followed by appropriate thermal treatments for cyclization reaction. BisAPAF-IC PHA with two different molecular weights (MWs) were synthesized from a low temperature polymerization of 2,2'-bis(3-amino-4-hydroxy-phenyl) hexafluoropropane (BisAPAF) and isophthaloyl chloride (IC). Using dimethylacetamide (DMAc) and tetrahydrofuran (THF), solvent effects oil the electrospinnability of PHA solutions were investigated. For balancing the solution properties, it was found that DMAc/THF mixture with a weight ratio of 1/9 was the best cosolvent to prepare smooth PHA fibers; uniform PHA fibers with a diameter of 325-720 nm were obtained by using 20 wt % PHA/(DMAc/THF) solutions. For a fixed PHA concentration, solutions with a lower MW of PHA yielded thinner electrospun fibers under the same electrospinning condition. After obtaining the electrospun BisAPAF-IC PHA fibers, subsequent thermal cyclization up to 350 degrees C produced the corresponding thermally stable BisAPAF-IC PBO fibers with a diameter of 305-645 nm. The structure of the precursor fibers and the fully cyclized fibers were characterized by FTIR. For the cyclized BisAPAF-IC PBO fibers, thermogravimetric analysis showed a 5% weight loss temperature at 523 degrees C in nitrogen atmosphere. The interconnected fiber structure in the BisAPAF-IC PBO fiber mats was irrelevant to the curing process, but resulted from the jet merging during the whipping process as revealed by the high speed camera images. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8159-8169, 2008