This Letter reports that the atomic corrugation of the surface can affect nanoscale interfacial adhesion and friction differently. Both atomic force microscopy (AFM) and molecular dynamics (MD) simulations showed that the adhesion force needed to separate a silica tip from a graphene step edge increases as the side wall of the tip approaches the step edge when the tip is on the lower terrace and decreases as the tip ascends or descends the step edge. However, the friction force measured with the same AFM tip moving across the step edge does not positively correlate with the measured adhesion, which implies that the conventional contact mechanics approach of correlating interfacial adhesion and friction could be invalid for surfaces with atomic-scale features. The chemical and physical origins for the observed discrepancy between adhesion and friction at the atomic step edge are discussed.