This study presents an ultrahigh-nickel layered cathode material, LiNi0.94Co0.05Te0.01O2, which addresses the critical issues of volume change and reduced oxygen stability in nickel-rich layered transition metal oxides. The introduction of high-valent tellurium cations (Te6+) into the cathode material enhances its performance by engineering the particle morphology and forming a stable Te–Ni–Te ordered superstructure. This structure tunes the ligand energy-level structure, suppressing lattice oxygen loss and improving structural stability. The material exhibits an initial capacity of 239 mAh g-1 and a capacity retention of 94.5% after 200 cycles. When used in a pouch cell with a silicon-carbon anode, it achieves a monomer energy density of 404 Wh kg-1 with a retention rate of 91.2% after 300 cycles. Advanced characterizations and theoretical calculations confirm that the Te–Ni–Te ordered structure effectively mitigates lattice strain and prevents cooperative lattice distortion, enhancing the stability of lattice oxygen. This work advances the energy density of nickel-based lithium-ion batteries to over 400 Wh kg-1 and suggests new opportunities for cathode material design without compromising performance and sustainability.This study presents an ultrahigh-nickel layered cathode material, LiNi0.94Co0.05Te0.01O2, which addresses the critical issues of volume change and reduced oxygen stability in nickel-rich layered transition metal oxides. The introduction of high-valent tellurium cations (Te6+) into the cathode material enhances its performance by engineering the particle morphology and forming a stable Te–Ni–Te ordered superstructure. This structure tunes the ligand energy-level structure, suppressing lattice oxygen loss and improving structural stability. The material exhibits an initial capacity of 239 mAh g-1 and a capacity retention of 94.5% after 200 cycles. When used in a pouch cell with a silicon-carbon anode, it achieves a monomer energy density of 404 Wh kg-1 with a retention rate of 91.2% after 300 cycles. Advanced characterizations and theoretical calculations confirm that the Te–Ni–Te ordered structure effectively mitigates lattice strain and prevents cooperative lattice distortion, enhancing the stability of lattice oxygen. This work advances the energy density of nickel-based lithium-ion batteries to over 400 Wh kg-1 and suggests new opportunities for cathode material design without compromising performance and sustainability.