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With the development of technical requirements, the current challenges faced by bearing materials mainly revolve around high-temperature conditions and the trend towards material lightweighting. Full ceramic bearings are the new candidate due to their excellent properties. This article details the tribological and adsorption performance of chlorophenyl silicone oil (CPSO) as a high-temperature lubricant in ceramic tribological systems (ZrO₂, Al₂O₃, and Si₃N₄). Among the three ceramic tribological systems, the lubrication performance can be ordered as Si₃N₄ > Al₂O₃ > ZrO₂, as the wear rates of the ZrO₂ and Al₂O₃ tribo-systems are almost 1135.67 and 283.33 times larger than that of the Si₃N₄ tribo-system, respectively. The observed results can be explained by the superior adsorption performance of CPSO on a Si₃N₄ ceramic surface, which was calculated by molecular dynamic simulation. The molecular dynamic simulation results show the adsorption energy of CPSO/Si₃N₄ is almost 54.09 and 61.18 times higher compared to that on ZrO₂ and Al₂O₃ ceramics. These findings provide experimental and theoretical insights for understanding the lubrication performance of CPSO in a full ceramic tribo-system.