A carbonyl-bridged single molecular precursor LiTM(acac)3 [transition metal (TM) = cobalt/manganese/nickel (Co/Mn/Ni), acac = acetylacetone], featuring a one-dimensional chain structure, was designed and applied to achieve the layered oxide cathode materials: LiTMO2 (TM = Ni/Mn/Co, NMC). As examples, layered oxides, primary LiCoO2, binary LiNi0.8Co0.2O2 and ternary LiNi0.5Mn0.3Co0.2O2 were successfully prepared to be used as cathode materials. When they are applied to lithium-ion batteries (LIBs), all exhibit good electrochemical performance because of their unique morphology and great uniformity of element distribution. This versatile precursor is predicted to accommodate many other metal cations, such as aluminum (Al3+), iron (Fe2+), and sodium (Na+), because of the flexibility of organic ligand, which not only facilitates the doping-modification of the NMC system, but also enables synthesis of Na-ion layered oxides. This opens a new direction of research for the synthesis of high-performance layered oxide cathode materials for LIBs.