Carbon-containing tribofilms have attracted significant interest in the lubrication research despite a scarcity of information on their high-temperature performance under severe boundary conditions. In this study, high-temperature lubrication of the carbon tribofilm produced from cyclopropane carboxylic acid (CPCa) and NiAl-layered double hydroxide (LDH) nanoparticles was evaluated. NiAl-LDH nanoparticles significantly enhanced the friction stability and antiwear performance of CPCa by over 90% at 50°C and 100°C, comparable to the benchmark zinc dialkyldithiophosphates (ZDDPs). The highly graphitic amorphous carbon tribofilms and the fine-grain intermediate tribolayer constructed by the thermal decomposition products of NiAl-LDH contributed to such excellent lubrication performance. This study paves a pathway in developing functional anti-wear additives for the durable and high-performance carbon-containing tribofilms at high temperatures.