The aerobic oxidation of ethylbenzene is an effective way to produce acetophenone, in which solvent-free conditions and oxygen as the sole oxidant are the best choice. At present, the catalytic activity and selectivity are still at an unsatisfactory level, because efficient catalysts need to achieve both C–H bond activation and O₂ activation. In this work, the 2-methylimidazole-induced hydrolysis strategy was used to prepare a new class of CoNi-layered double hydroxide (CoNi-LDH) materials with different metal ratios. High-Resolution Transmission Electron Microscopy (HRTEM) showed that CoNi-LDH had obvious weak crystallinity and a thin lamellar structure. X-ray Photoelectron Spectroscopy (XPS) reveals the consistency between the content of the M–O component in the host layer and the proportion of Co³⁺, among which CoNi-LDH with a feed ratio (Co : Ni) of 2 : 1 (Co₂Ni-LDH) has the highest M–O content and Co³⁺ ratio. The formation of M–O is due to the H-vacancy generated by the breaking of the hydroxyl group, which can be used for the H abstraction of C–H bonds. The redox effect caused by M²⁺/M³⁺ facilitates the transfer of electrons, which promotes the activation of O₂ to the superoxide radical anion (˙O₂⁻). Thereby, Co₂Ni-LDH shows the highest catalytic activity for the oxidation of ethylbenzene. Under solvent-free conditions and with oxygen as the sole oxidant, 97.8% conversion of ethylbenzene and 98.8% selectivity of acetophenone can be obtained. The excellent catalytic performance is related to the structure of CoNi-LDH, and is also the best when compared with the reported results. Various types of aromatic hydrocarbons containing benzyl C–H bonds can be effectively oxidized by CoNi-LDH to produce the corresponding ketone products.