The formation of homojunctions and heterojunctions on two-dimensional (2D) substrates plays a key role in the device performance of thin films. Accelerating the progress of device fabrication in nanowires (NWs) also necessitates a similar understanding in the one-dimensional (1D) system. Nanohomojunction (GaN on GaN) and nanoheterojunction (InN on GaN) nanorods (NRs) were formed in a two-step growth process by a vapor–liquid–solid (VLS) mechanism. Ga2O3 nanoribbons were formed using Ni as catalyst in a chemical vapor deposition (CVD) technique and then completely converted to GaN NWs with NH3 as reactant gas. An Au catalyst is used in the second step of the VLS process to grow GaN and InN NRs on GaN NWs using CVD techniques. A morphological study showed the formation of nanobrushes with different structural symmetries and sub-symmetries in both homogeneous and heterogeneous systems. Structural characterizations showed nearly defect-free growth of nanohomojunction (GaN) and nanoheterojunction (InN) NRs on 1D GaN NW substrates.