Metal–organic framework (MOF) nanoparticles exhibit potential as lubrication additives owing to their physical, mechanical, and chemical effects. However, studies on their solid lubrication properties, particularly those of three-dimensional (3D) MOF materials in liquid-free environments, have rarely been reported. This work introduces the synergistic interaction between the substrate roughness and particle loading quantity in the case of the Zr-based 3D MOF, UiO-66-NH 2. UiO-66-NH 2 achieves a twofold friction reduction compared with an Al pin-on-Al substrate under ambient temperature and humidity. In addition, it demonstrates a reduced Al substrate roughness, resulting in early-stage termination of solid lubrication effects. Scanning electron microscopy (SEM) indicates that UiO-66-NH 2 has an engineered Al surface coating, and its particles transition from interfacial sliding to rolling friction. To verify the practical applicability of UiO-66-NH 2 as a solid lubrication material, it is applied to a triboelectric nanogenerator (TENG) for electrical energy harvesting. The TENG with UiO-66-NH 2 exhibits not only a stable output voltage for 50,000 s but also a significant increase in the root-mean-squared voltage and current of 13.66% and 5.66%, respectively. This study provides new insights into the design principles of 3D MOF-based solid lubricants for advanced tribological and energy devices.