We have grown homoepitaxial GaN nanowall networks on GaN template using an ultra-high vacuum laser assisted molecular beam epitaxy system by ablating solid GaN target under a constant r.f. nitrogen plasma ambient. The effect of laser repetition rate in the range of 10 to 30 Hz on the structural properties of the GaN nanostructures has been studied using high resolution X-ray diffraction, field emission scanning electron microscopy and Raman spectroscopy. The variation of the laser repetition rate affected the tip width and pore size of the nanowall networks. The z-profile Raman spectroscopy measurements revealed the GaN nanowall network retained the same strain present in the GaN template. The optical properties of these GaN nanowall networks have been studied using photoluminescence and ultrafast spectroscopy and an enhancement of optical band gap has been observed for the nanowalls having a tip width of 10–15 nm due to the quantum carrier confinement effect at the wall edges. The electronic structure of the GaN nanowall networks has been studied using X-ray photoemission spectroscopy and it has been compared to the GaN template. The calculated Ga/N ratio is largest (∼2) for the GaN nanowall network grown at 30 Hz. Surface band bending decreases for the nanowall network with the lowest tip width. The homoepitaxial growth of porous GaN nanowall networks holds promise for the design of nitride based sensor devices.