Safe and high-capacity cathode materials are a long quest for commercial lithium-ion battery development. Among various searched cathode materials, Li2FeSiO4 has taken the attention due to optimal working voltage, high elemental abundance, and low toxicity. However, as per our understanding and observation, the electrochemical performance of this material is significantly limited by the intrinsic low electronic conductivity and slow lithium-ion diffusion, which limits the practical capacity (a theoretical value of ∼330 mAh g-1). In this report, using first-principles density functional theory based approach, we demonstrate that chlorine doping on oxygen site can enhance the electronic conductivity of the electrode and concurrently improve the electrochemical performance. Experimentally, X-ray diffraction, X-ray photoelectron spectroscopy, and field-emission gun scanning electron microscopy elemental mapping confirms Cl doping in Li2-xFeSiO4-xClx/C (x ≤ 0.1), while electrochemical cycling performance demonstrated improved performance. The theoretical and experimental studies collectively predict that, via Cl doping, the lithium deinsertion voltage associated with the Fe2+/Fe3+ and Fe3+/Fe4+ redox couples can be reduced and electronic conductivity can be enhanced, which opens up the possibility of utilization of silicate-based cathode with carbonate-based commercial electrolyte. In view of potential and electronic conductivity benefits, our results indicate that Cl doping can be a promising low-cost method to improve the electrochemical performance of silicate-based cathode materials. © 2017 American Chemical Society.