In the present work, Black Phosphorus Quantum Dots (BPQDs) were synthesized via sonication-assisted liquid-phase exfoliation. The average size of the BPQDs was 3.3 ± 0.85 nm. The BPQDs exhibited excellent dispersion stability in ultrapure water. Macroscale superlubricity was realized with the unmodified BPQDs on rough Si3N4/SiO2 interfaces. A minimum coefficient of friction (COF) of 0.0022 was achieved at the concentration of 0.015 wt%. In addition, the glycerol was introduced to promote the stability of the superlubricity state. The COF of the BPQDs-Glycerol aqueous solution (BGaq) was 83.75% lower than that of the Glycerol aqueous solution (Gaq). Based on the above analysis, the lubrication model was presented. The hydrogen-bonded network and silica gel layer were formed on the friction interface, which played a major role in the realization of macroscale superlubricity. In addition, the adsorption water layer could also prevent the worn surfaces from making contact with each other. Moreover, the synergistic effect between BPQDs and glycerol could significantly decrease the COF and maintain the superlubricity state. The findings theoretically support the realization of macroscale superlubricity with unmodified BPQDs as a water-based lubrication additive.