Nanotribology has been given increasing attention by researchers in pursuing the nature of friction. In the present work, an approach that combines the supramolecular assembly and nanotribology is introduced. Herein, the nano-tribological study was carried out on seven supramolecular template networks [namely, hydrogen bond induced tricarboxylic acids and van der Waals force induced hexaphenylbenzene (HPB) derivatives]. The template networks, as well as the host-guest assemblies of template molecules induced by different forces, were constructed on the highly oriented pyrolytic graphite (HOPG) surface and explicitly characterized using scanning tunneling microscopy (STM). Meanwhile, the nanotribological properties of the template networks were measured using atomic force microscopy (AFM). Together with the theoretical calculation using the density functional theory (DFT) method, it was revealed that the friction coefficients were positively correlated with the interaction strength. The frictional energy dissipation mainly derives from both the intermolecular interaction energy and the interaction energy between molecules and the substrate. The efforts not only help us gain insight into the competitive mechanisms of hydrogen bond and van der Waals force in supramolecular assembly but also shed light on the origin of friction and the relationship between the assembly structures and the nanotribological properties at the molecular level.