The pursuit of high-energy-density cathode materials has positioned LiNiO₂ as a promising candidate due to its high theoretical capacity. However, its practical application is hindered by structural instability, cation mixing, and sluggish Li-ion mobility. This study presents a strategic co-doping approach to enhance the electrochemical performance of R3m-structured LiNiO₂ by introducing Na at the Li site and Nb/Al at the Ni site. First-principles calculations based on density functional theory (DFT), combined with the bond valence sum energy (BVSE) method, were employed to evaluate the structural, electronic, and transport properties of the doped systems. The optimized lattice parameters reveal that co-doping induces lattice expansion and suppresses cation disorder, thereby improving structural integrity. Band structure analysis indicates a reduced band gap in the co-doped configurations, suggesting enhanced electronic conductivity. Bader charge analysis confirms charge redistribution between dopants and host atoms, which stabilizes Ni oxidation states and mitigates Jahn–Teller distortion. Formation energy and phonon dispersion calculations validate the thermodynamic and dynamic stability of the modified structures. Furthermore, BVSE-based ion migration mapping shows that Na/Nb and Na/Al co-doping significantly broadens Li-ion diffusion pathways and lowers migration barriers compared to pristine LiNiO₂. These results demonstrate that dual-site doping is an effective strategy to overcome intrinsic limitations of Ni-rich layered oxides, offering a rational design route for next-generation Li-ion battery cathodes with improved cycling stability and rate capability.