Trace doping is an efficient way to improve the stability of nickel-rich layered cathodes for lithium-ion batteries, but the structural origin of such improvement, rather than a simple replacement, has been rarely explored. Herein, Ga dopants have been introduced into a nickel-rich host, LiNi0.9Co0.1O2, by a combination of coprecipitation and the solid-state sintering method. Structural analyses based on high-resolution synchrotron powder diffraction data and X-ray absorption spectra suggest that Ga preferentially sits in the NiO6 slabs, resulting in reduced Ni/Li cationic mixing and depressed lattice vibration. Due to the smaller dissociation energy of Ga-O bonds, some Ga3+ cations migrate first toward Li layers upon delithiation and form the GaO4 tetrahedral symmetry irreversibly during the electrochemical process, which acts as a pillar in the subsequent electrochemical processes. As a result, the doped material exhibits both improved cycling performance and rate capability under a high operating voltage (4.5 V) due to the stabilized structure in the lithiation/delithiation process. This study illustrates how a dopant enhances the electrochemical stability in views of both pristine and charged structure and suggests that a positive effect is expected from the dopant favoring the tetrahedral symmetry (e.g., Al).