Advances in nano-lubricant additives are vital to the pursuit of energy efficiency and sustainable development. Carbon dots (CDs) have been widely investigated in the domain of lubricant additives owing to their extraordinary tribological properties, in particular, their friction-reducing and anti-wear properties. Metal-doped CDs are a new type of CDs, and their friction-reducing and anti-wear properties are attracting increasing attention. Therefore, a series of CDs doped with various divalent metal ions have been successfully synthesized via one-pot pyrolysis. The tribological properties of the synthesized CDs as water-based lubricant additives are in the following order: Zn-CDs > Cu-CDs ≫ Mg-CDs > Fe-CDs > U-CDs. Specifically, adding 1.0 wt% of Zn-CDs into water-based lubricant results in 62.5% friction and 81.8% wear reduction. Meanwhile, the load-carrying capacity of the water-based lubricant increases from 120 N to at least 500 N. Zn-CDs as an additive have long service life. Additionally, anion-tuned Zn-CDs fabricated via anion exchange exhibit promise as lubricant additives for poly(ethylene glycol). Based on the results of wear scar surface analyses, it is discovered that tribochemical films, primarily composed of iron oxides, nitrides, metal carbonates, zinc oxides, zinc carbonates, organic compounds, and embedded carbon cores, formed on the rubbing surfaces with a thickness of approximately 270 nm when Zn-CDs are used as additives. This film combined with the “ball-bearing” and third-particle effects of Zn-CDs contributed to excellent lubrication performance.