The tribological performances of fullerenol and nanodiamonds (NDs) as additives in water-based lubricants for amorphous carbon (a-C) coatings are investigated to avoid disadvantage factors, such as chemical reactions and deformation of particles. The effects of size and additive amount on tribological properties of nanoparticles are studied by rigid nanoparticles within the dot size range. The results show that owing to its small particle size (1–2 nm), fullerenol cannot prevent direct contact of the friction pair at low concentration conditions. Only when the quantity of fullerenol increased to support the asperity contact loads in sufficient concentration did nano-bearings perform well in anti-friction and anti-wear effects. Unlike fullerenol, nanodiamond particles with a diameter of about 5–10 nm show friction-reducing effect based on the nano-bearing effects at ultra-low concentration (0.01 wt.%), whereas particles at higher concentration block the rolling movement, hence increasing the coefficient of friction (COF) and wear. As a result of the effect of difference in size, fullerenol provides a better overall lubrication, but it is hard to reach a friction coefficient as low as NDs even under the optimal conditions.