Layered Co-free Ni-rich cathodes are the most cost-effective for high-energy-density Li-ion batteries (LIBs), yet the structural instability and interfacial side reactions seriously hamper their commercial applications versus the Co-contained counterpart. Herein, a synchronous Ge-doping and Li4GeO4-coating of the Co-free Ni-rich cathodes have been realized to tackle these limitations during high-temperature lithiation of the corresponding hydroxide precursors. The nonmagnetic Ge4+ doping effectively relieves the magnetic frustration and the lattice oxygen loss with reduced cation mixing and gas emission. The Li-ion conductive and anti-erosive Li4GeO4 coatings contribute to enhance the surface chemistry stability and Li-ion migration interface kinetics. Consequently, the resulting Co-free Ni-rich cathodes delivers a high reversable capacity of 223.3 mAh g−1 at 0.1 C and maintains 127.5 mAh g−1 even at 10C within 2.7–4.4 V. More impressively, it displays high-capacity retention of 90.5% in coin-type half-cell after 150 cycles and 80.5% in pouch-type full-cell after 500 cycles at 3C, demonstrating a long-term cycle life.