The thermolysis of 2,4,6[(CH3)(2)N](3)B3N3H3 (1), 2,4[(CH3)(2)N](2)-6-(CH3HN)B3N3H3 (2), and 2-[(CH3)(2)N]-4,6-(CH3HN)(2)B-3-N3H3 (3) led to polyborazines 4, 5, and 6 respectively. The polymers display direct B-N bonds between borazinic B3N3 rings and. in addition, a proportion of -N(CH3)- bridges for 5 and 6, as clearly underlined by C-13 NMR spectroscopy. Melt-spinning of these three polymeric precursors exemplified that their ease of processing increases in the order 4 < 5 < 6. Nevertheless, polyborazine filaments could be prepared from each of them and a subsequent thermal treatment up to 1800degreesC resulted in the formation of crystalline hexagonal boron nitride fibers, which were characterized by X-ray diffraction analysis, Fourier transform infrared (FTIR) spectroscopy, and Raman spectroscopy. Scanning electron microscopy (SEM) images showed that the ceramic fibers are circular and dense without major defects. The mechanical properties for 4-derived fibers could not be measured because of their brittleness. whereas measurements on 5- and 6-derived fibers gave tensile strength a sigma(R) = 0.51 GPa, Young's modulus E = 67 GPa, and sigma(R) = 0.69 GPa, E = 170 GPa. respectively. The improvement in mechanical properties for ceramic fibers prepared respectively from 4, 5, and 6 could be explained to a large extent by the improvement of the processing properties of the preceramic polymers. This evolution could be related to the increased ratio of bridging -N(CH3)- groups between the B3N3 rings within the polymers 4, 5, and 6 and therefore to the functionalities of the starting monomers 1, 2, and 3.