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
1 0 1¯ 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.