The electrochemical performance of LiGa_yCo_1−yO₂ electrodes_,y=0.005 and 0.1, was studied. Charge/discharge curves in galvanostatic condition were obtained for a series of voltages ranging from 4.35 to 4.7V. Samples were previously characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR), X-ray absorption spectroscopy (XAS) and conductivity measurements. Comparison of data obtained for LiGa_yCo_1−yO₂ and the pristine oxide LiCoO₂ is provided. Ga doping at 0.5mol% drastically reduces the electrode capacity fading when charges at 4.35 or 4.5V are applied, while Ga doping at 10mol% spoils the Ga-doped oxides electrochemical response, even at a cut-off limit of 4.35V. These positive and negative effects were attributed to changes in both the electronic conductivity and local structure of LiCoO₂, induced by substitution of Co for Ga and cationic disorder. For y=0.005, a slight distortion in the LiCoO₂ local structure occurs, and formation of states in the band gap that the raise oxide electronic conductivity is observed, explaining the electrochemical improvement in LiGa_yCo_1−yO₂. In contrast, hybridization with oxygen occurs when y=0.1, opening LiCoO₂ band gap and making LiGa_yCo_1−yO₂ an insulator and a cationic disorder material that leads to poor electrochemical performance. Finally, XAS results show that Ga doping does not change the LiCoO₂ charge transfer mechanisms, where oxygen is reduced during lithium extraction.