The lithium-ion battery, a major renewable power source, has been widely applied in portable electronic devices and extended to hybrid electric vehicles and all-electric vehicles. One of the main issues for the transportation application is the need to develop high-performance cathode materials. Here we report a novel nanostructured cathode material based on air-stable polycrystalline Li0.28Co0.29Ni0.30Mn0.20O2 thin film with lithium deficiency for high-energy density lithium-ion batteries. This film is prepared via a method combining radio frequency magnetron sputtering and annealing using a crystalline and stoichiometric LiCo1/3Ni1/3Mn1/3O2 target. This lithium-deficient Li0.28Co0.29Ni0.30Mn0.20O2 thin film has a polycrystalline nanostructure, high tap density, and higher energy and power density compared to the initial stoichiometric LiCo1/3Ni1/3Mn1/3O2. Such a material is a promising cathode candidate for high-energy lithium-ion batteries, especially thin-film batteries.