<p>Ultra-low friction, including superlubricity (near-zero friction), has been predicted for a recently synthesized, two-dimensional (2D) monolayer fullerene network sliding over a graphene substrate, highlighting its potential to reduce energy consumption and extend the lifetime of mechanical systems. However, how friction depends on the stacking angle between the 2D fullerene and graphene—and in particular, its microscopic origin—remains unclear. Through extensive molecular dynamics simulations, we demonstrate that friction at the 2D fullerene–graphene interface exhibits strong angular dependence, with friction coefficients ranging from 10^–5 to 10^–1, which can be attributed to distinct fluctuations in atomic registry during the sliding process. Interfacial atomic-level force analysis further reveals that the variation in friction stems from changes in the number of atoms within the contact region that serve either as pinning sites to resist lateral sliding or as pushing points to facilitate it. We also show that the frictional behavior of the system can be tuned by modifying substrate stiffness, sliding velocity, and temperature. These insights provide guidelines for designing robust low-friction interfaces in advanced materials and devices.</p>