Morphological control of poly(2,5-benzimidazole) (PBI) was examined by reaction-induced phase separation of oligomers during polymerization to prepare nanofibers. Three monomers, 3,4-diaminobenzoic acid (DABA), 3,4-diacetoamidebenzoic acid (DAcBA) and phenyl 3,4-diaminobenzoate (PDAB), were used to synthesize PBI. Polymerizations were carried out at 350 degrees C in a mixture of dibenzyltoluene isomers. Polymerization of DABA yielded spheres with plate-like crystals on their surface. Polymerization of DAcBA yielded almost no precipitates because of the high solubility of DAcBA oligomers. By contrast, polymerization of PDAB yielded aggregates of PBI nanofibers (of which the average diameter was similar to 60 nm), which resembled nonwoven fabrics. These fibers were formed by precipitation of (2,5-benzimidazole) oligomers and their subsequent polymerization into a developing crystal structure. The structure of the monomer significantly influenced the morphology of the PBI product, and PDAB was preferable for the preparation of PBI nanofibers. The temperature of 10% N-2 weight loss in these nanofibers was in the range of 634-644 degrees C and they were thermally stable. Polymer Journal (2010) 42, 375-382; doi:10.1038/pj.2010.20; published online 17 March 2010