Superlubricity has been recognized as the future of tribology. However, it is hard to achieve superlubricity under extreme conditions such as a high load and low sliding speed on the macroscale. In this paper, a remarkable synergetic lubricating effect between nanoparticles and silicon nitride (Si3N4) is demonstrated; this effect helps water-lubricated Si3N4 achieve superlubricity under extreme conditions successfully. Different kinds of hairy silica nanoparticles were prepared, dispersed into water, and characterized using a variety of methods. The tribological properties of water-lubricated Si3N4 with nanoparticle additives were tested using a ball-on-disk tribometer under different loads and sliding speeds. The coefficient of friction and wear scar diameter were measured and analyzed. Both the nanoparticle size and surface functional groups have a significant influence on the tribological properties of water-lubricated Si3N4. Amino-modified silica nanoparticles reduce the friction coefficient of water-lubricated Si3N4 by 82.9% under 60 N, compared with that achieved using deionized water, and induce superlubricity after the running-in process. Silica nanoparticles effectively form a homogenous film with silica gel on the worn surface under a high load and thus reduce the wear and maintain the superlubricity under extreme conditions.