Potassium hydroxide solution was used to etch un-doped GaN grown on the sapphire substrate at 180 and 260 °C. We illustrated the etching phenomenon in detail and probed its mechanism in the wet etching process. By multiplying the planar density and the number of dangling bonds on the N atom, we proposed the etching barrier index (EBI) to describe the difficulty degree of each lattice facet. The raking of EBI will be +c-plane > a-plane > m-plane > −c-plane > (10-1-1) plane > r-plane. Combining the EBI with SEM results, we thoroughly studied the whole etching process. We confirmed that in our research, KOH wet etching on GaN starts from the r-plane instead of the +c-plane or −c-plane, which differs from other studies. We also found that during the high-temperature etching process, there are two etching approaches. In one, the etching begins vertically from the top to the bottom, then horizontally, and finally reversely from the bottom to the top. In the other, etching pits will develop into a hexagonal hole of the sidewall of m-plane.