Mesoporous silica nanoparticles (MSNs) were firstly utilized as the delivery vehicles of antioxidant 2-mercaptobenzimidazole (MB) to fabricate highly anti-aging styrene-butadiene rubber (SBR) composites. The thermo-oxidative aging behaviour of SBR composites was systematically evaluated by mechanical testing, FTIR and XPS. For the composites with MSNs-MB and free MB, though some of free MB were consumed or migrated to the elastomer surface, the released MB from MSNs-MB steadily migrated to the free rubber phase to ensure a continuous and stable antioxidant supply for a long time. Therefore, the SBR composites with binary protection from MSNs-MB and free MB exhibited superior thermo-oxidative stability than the SBR composites with only free MB. This work proposed a reliable approach to resolve the “blooming” defects of antioxidants and extend the service life of the elastomer products, which may open up a new route for the rational design and construction of highly anti-aging elastomer composites.