The objective of this study was to investigate the roles and tribological mechanisms of onion-like carbon nanoparticles derived from biodiesel soot (BDS) when applied in water (H2O) and liquid paraffin (LP). In this study, we prepared nitric acid-treated BDS (NA-BDS) as an additive to H2O and NA-BDS modified with oleylamine (NA-BDS-OLA) as an additive to LP. Raman spectroscopy, field-emission transmission electron microscopy, Fourier transform infrared spectroscopy, and zeta potentiometry were used to characterize the results of the nitric acid treatment and oleylamine modification. The tribological behaviors and corresponding mechanisms of the new onion-like carbon nanoparticles were evaluated using a ball-on-disc reciprocating tribometer, as well as field-emission scanning electron microscopy, three-dimensional laser scanning microscopy, and Raman spectroscopy. The results indicated that the additives NA-BDS and NA-BDS-OLA, which were onion-like carbon nanoparticles with sizes ranging from 35 to 40 nm, enhanced the antiwear and friction reduction properties of H2O and LP, respectively. Through tribo-mechanisms, these types of soot can serve as spacers and ball bearings between the rubbing surfaces. Moreover, exfoliation under a high load as a result of the formation of a graphitic layer facilitates easy shearing.