Organic molybdenum lubricant additive like molybdenum dialkyl dithiocarbamate (MoDTC) can cause wear acceleration of diamond-like carbon (DLC) coating coupled with steel under boundary lubrication, which hinders its industrial application. Therefore, polyisobutylene succinimide (PIBS), an organo molybdenum amide, was adopted to modify molybdenum oxide affording molybdenum polyisobutylene succinimide-molybdenum oxide nanoparticles (MPIBS-MONPs) with potential to prevent the wear acceleration of DLC coating. The thermal stability of MPIBS-MONPs was evaluated by thermogravimetric analysis. Their tribological properties as the additives in di-isooctyl sebacate (DIOS) were evaluated with MoDTC as a control; and their tribomechanism was investigated in relation to their tribochemical reactions and synergistic tribological effect with zinc dialkyldithiophosphate (ZDDP) as well as worn surface characterizations. Findings indicate that MPIBS-MONPs/ZDDP added in DIOS can significantly reduce the friction and wear of DLC coating, being much superior to MoDTC. This is because MPIBS-MONPs and ZDDP jointly take part in tribochemical reactions to form a composite tribofilm that can increase the wear resistance of DLC coating. Namely, the molybdenum amide on MPIBS-MONPs surface can react with ZDDP to form MoS2 film with excellent friction-reducing ability; and MPIBS-MONPs can release molybdenum oxide nanoparticle to form deposited lubrication layer on worn surfaces. The as-formed composite tribofilm consisting of molybdenum oxide nanocrystal, amorphous polyphosphate, and molybdenum disulfide as well as a small amount of Mo2C accounts for the increase in the wear resistance of DLC coating under boundary lubrication.