Lithium- and manganese-rich layered oxide (LMRO) is considered a promising cathode material for lithium-ion batteries owing to its high capacity and energy density. However, operation at a high voltage of 4.8 V leads to several issues including low Coulombic efficiency, poor cycle life, slow kinetics, and voltage decay due to spinel phase transition, hindering commercialization. Herein, we synthesized a cobalt-free LMRO cathode and studied the effect of Nb2O5 and Sb2O3 coating layers on electrochemical performance. The Nb2O5 coating facilitated the formation of a LiNbO3 layer, which enhanced the initial electrochemical performance, including Coulombic efficiency and energy density. Meanwhile, Sb2O3 not only coated the surface but also doped into the bulk structure, thereby increasing capacity and improving rate capability. Comparative analysis using materials with different structural solubility revealed how oxide coatings influenced lithium-ion transport and electrochemical behavior. This study highlights the importance of interfacial engineering for optimizing LMRO cathodes for high-performance lithium-ion batteries.