Li-rich　layered　oxides　(LLOs)　are　fascinating　high-energy　cathodes　for　lithium-ion　batteries　(LIBs),　but　still　suffer　from　critical　drawbacks　that　retard　their　practical　applications.　Although　surface　modification　is　effective　to　protect　LLOs　from　structural　deterioration,　the　delicate　design　of　structures　on　a　grain　surface　with　promising　scalability　for　industrial　application　is　still　challenging.　Herein,　using　the　atomic　layer　deposition　(ALD)　technique,　a　composite　nanostructure　comprising　a　uniform　LiTaO3　coating　layer　(approximate　to　3　nm)　and　a　spinel　interlayer　structure　(approximate　to　1　nm)　is　constructed　on　the　grain　surface　of　industrial　LLO　(Li1.13Mn0.517Ni0.256Co0.097O2)　agglomerated　spheres.　The　surface　composite　nanostructure　can　not　only　enhance　the　structural/interfacial　stability　of　the　LLO,　but　also　facilitates　Li+　diffusion,　thereby　significantly　improving　its　cycle　stability,　rate　performance,　thermal　stability,　and　voltage　maintenance.　Specifically,　the　LLO　coated　with　10　ALD　cycles　exhibits　a　small　voltage　decay　rate　of　0.9　mV　per　cycle,　a　reversible　capacity　of　272.8　mAh　g(-1)　at　0.1　C,　and　a　capacity　retention　of　85%　after　200　cycles　at　1　C,　suggesting　the　important　role　of　surface　composite　nanostructure　for　improving　the　electrochemical　performance.　This　work　provides　new　insights　into　the　composite　nanostructure　design　on　the　grain　surface　of　cathode　materials　for　high-performance　LIBs.