The relentless march of scientific and technological advancements has led to a surge in demand for more efficient lubrication technologies. The limitations of conventional single-method lubrication are becoming increasingly apparent, as they fail to fully address the industrial need to reduce friction and wear, extend equipment life spans, and enhance production capabilities. In response to the pressing dual challenges of enhancing lubrication effectiveness and upholding environmental standards, there is a growing impetus to advance the research and development of coating materials and green additives. Addressing the issues of friction and wear at interfaces through establishing a highly efficient carbon-based coating/additive/ base oil ternary system, is poised to emerge as a superior option for the future of lubrication and anti-wear technology. In this work, a fullerene-like carbon-based (FLC) coating and a layered porous aromatic framework carbon-based (LPAF) additive were prepared by plasma-enhanced chemical vapor deposition (PECVD) and Sonogashira-Hagihara coupling reaction, respectively. On this basis, a ternary composite lubrication system composed of an FLC coating, LPAF additive and PAO base oil was constructed. The tribological behavior of the ternary system was investigated systematically and the potential friction mechanism was proposed. The LPAF additive was a multi-layer material that was stacked with amorphous carbon monolayers, which made LPAF have good stripping properties and laid a foundation for its good anti-friction and anti-wear properties. Observations indicated that the FLC-PAO system exhibited an average friction coefficient of approximately 0.083, with a corresponding wear rate of around 6.0×10–9 mm3/(N.m). The incorporation of 1.0% LPAF into PAO10 base oil significantly reduced the average friction coefficient of the FLC-PAO-LPAF system to about 0.016, while the wear rate was diminished to 1.7×10–9 mm3/(N.m). These findings underscored the substantial benefits of LPAF as an additive in enhancing the tribological properties of the composite system. An in-depth examination of the influence of additive concentration, load, and friction velocity on the tribological behavior of the FLC-PAO-LPAF system revealed that optimal performance was achievable under the right concentration and testing conditions. Nonetheless, under more challenging environmental conditions, the efficacy of the FLC-PAO-LPAF ternary system was compromised, reverting to a performance level comparable to that of the FLC-PAO binary system. Post-friction analysis confirmed that LPAF, with its characteristic amorphous microstructure, underwent a series of tribochemical reactions at the friction interfaces and was transformed into onion-like carbon flakes through graphitization. The layered structure of the friction products was pivotal in further reducing friction in the ternary composite system. A large number of graphite-like phases were deposited between the friction interfaces to form carbon-based transfer films, effectively stabilizing the friction coefficient at a low level, thereby endowing the FLC-PAO-LPAF ternary composite system with outstanding tribological properties. The green and environmental LPAF additive can significantly improve the tribological properties of the solid-oil composite lubrication system based on the carbon-based coating and base oil. The design strategy of terpolymer composite lubrication systems has expanded a new research field and an idea for further research and promoting the innovation and development of green and environmental solid-liquid composite lubrication technology. The program not only enriches the theoretical framework of lubrication technology, but also provides valuable intellectual support and motivation to promote sustainable development practice.