Surface　modification　is　an　effective　approach　for　overcoming　the　interfacial　degradations　to　enable　high　electrochemical　performance　of　battery　materials,　yet　it　is　still　challenging　to　realize　high-quality　surface　modification　with　simple　processing,　low　cost,　and　mass　production.　Herein,　a　thermal-induced　surface　precipitation　phenomenon　is　reported　in　a　Ti-dopped　LiCoO2,　which　can　realize　an　ultrathin　(approximate　to　5　nm)　and　uniform　surface　modification　by　a　simple　annealing　process.　It　is　revealed　that　surface　Li-deficiency　enables　bulk　Ti　to　precipitate　and　segregate　on　the　non-(003)　surface　facets,　forming　a　Ti-enriched　disordered　layered　structure.　Such　a　surface　modification　layer　can　not　only　stabilize　the　interfacial　chemistry　but　also　significantly　improve　the　charge/discharge　reaction　kinetics,　leading　to　much-improved　cycling　stability　and　rate　capability.　Dopants　surface　precipitation　is　a　unique　outward　diffusion　process,　which　differs　from　the　current　surface　modification　techniques　and　further　diversifies　these　approaches　for　realizing　high-quality　surface　modification　of　battery　materials.