In the current research, an easy and inexpensive method is used to synthesize highly crystalline gallium nitride (GaN) nanowires (NWs) on two different substrates [i.e., porous zinc oxide (PZnO) and porous gallium nitride (PGaN)] on Si (111) wafer by thermal evaporation without any catalyst. Microstructural studies by scanning electron microscopy and transmission electron microscope measurements reveal the role of the substrates in the nucleation and alignment of the GaN NWs. Further structural and optical characterizations were performed using high-resolution X-ray diffraction, energy-dispersive X-ray spectroscopy, and photoluminescence spectroscopy. Results indicate that the NWs have a single-crystal hexagonal GaN structure and growth direction in the (0001) plane. The quality and density of GaN NWs grown on different substrates are highly dependent on the lattice mismatch between the NWs and their substrates. Results indicate that NWs grown on PGaN have better quality and higher density compared to NWs on PZnO.