The structure transformations have been studied by X ray diffraction (XRD) and radial distribution function (RDF). Chemistry titration has been employed to determine residual B
2O
3 content in the BN fibers. The results show that the boron nitride fibers mainly consisted of turbostrastic structure with some hexagonal phase and rhombohedral phase after nitriding at 1100℃, and the main crystallization phase in fibers was affirmed as rhombohedral phase after 1800℃ in nitrogen atmosphere.