In this work, multi-walled carbon nanotubes (CNTs) were noncovalently functionalized with different amount of polymethylphenylsiloxane (PMPS) successfully, and then the products named as PMPS-1/CNTs, PMPS-2/CNTs and PMPS-3/CNTs, respectively, were introduced into silicone rubber (SR) to prepare a series of SR-based composites. Subsequent characterizations were used to analyze the noncovalent functionalization in addition to the thermal oxidative stability and mechanical properties of SR-based composites. The results showed that PMPS was wrapped on CNTs via physical absorption. PMPS/CNTs had good dispersibility in ethanol, and the solutions could remain stable without any visible precipitation even for 6 months. The physical absorption was thought to mainly result from π–π stacking, CH–π interactions and the van der Waals force between PMPS and the sp2 hybridized network of CNTs. Both the thermal oxidative stability and mechanical properties of PMPS/CNTs/SR composites before and after thermal oxidative aging could be improved by noncovalent functionalization of PMPS. For example, compared with CNTs/SR, the tensile strength before and after thermal oxidative aging of PMPS-2/CNTs/SR could be improved by 13 and 62%, respectively. Moreover, it was found that only the appropriate amount of PMPS can maximize the enhancement of noncovalent functionalization.