Nitrile butadiene rubber (NBR) is a water-lubricated bearing material with excellent vibrational absorption and impact resistance properties. However, its rapid wear under abnormal conditions is still a serious problem that needs to be solved. In this study, silica 69 (TESPT) was grafted onto the hydroxyl groups on the SiO2 surface to increase its interfacial interactions with NBR, and a molecular dynamics simulation method was employed to investigate how these interactions influence the tribological properties of NBR. The results showed that the introduction of SiO2 or SiO2(TESPT) significantly improved the mechanical properties and wear properties of NBR, but these fillers had little effect on the friction behavior of NBR. Compared with SiO2, SiO2(TESPT) exhibited stronger interfacial bonding with NBR, which further enhanced the van der Waals forces between NBR molecular chains. During the friction process, stronger interfacial interactions more effectively reduce the flexibility of the NBR molecular chains and the concentration of NBR atoms around the copper bar, thus reducing the binding energy between the copper bar and the polymer. These phenomena and the strong van der Waals interactions between NBR molecular chains can hinder the detachment of NBR chains (i.e., reduce the wear-induced atomic loss) and further improve the wear performance of NBR-based materials.