Severe melt-back etching has forced the epitaxy of GaN on Si to use an AlN buffer layer for growing high-quality two-dimensional layers, despite its high resistivity. Herein, we report a metal-based pre-orienting layer (POL) for growing GaN nanostructures (NSs) to replace the traditional AlN buffer layer. Two metals, titanium (Ti) and hafnium (Hf), were evaluated as POLs. We succeeded in fabricating arrays of GaN NSs with highly preferred orientation using selective-area growth. The crystallographic phase of the POLs critically affected the evolved orientation of the crystals. Photoluminescence measurements revealed that GaN NSs with Hf-based POLs were of reasonably high quality. We believe that this result will facilitate broader III-V semiconductor applications using alternative substrates moving beyond conventional Si-based optoelectronics.