Three-dimensional (3D) dendrite-like GaN nanostructures with sixfold symmetry branches were synthesized by a secondary Au-catalyzed vapor-liquid-solid (VLS) growth process. X-ray diffraction (XRD) analysis reveals that the as-grown GaN is wurtzite structure. The dendrite-like nanostructures resulted from the branches growth along the six crystallographically equivalent directions of < 10 (1) over bar 0 > in a < 0 0 0 1 > oriented GaN stem nanowire. The growth model was established and discussed according to the experimental results. Raman scattering spectrums were measured and the differences in Raman spectrums between the first- and second-synthesized products were discussed. (C) 2007 Published by Elsevier B.V.