Cu nanoparticles surface-modified by dioctylamine dithiocarbamate (DTC8) were synthesized using a two-phase extraction route. The size, morphology and structure of resultant surface-capped Cu nanoparticles (coded as DTC8-Cu) were analyzed by means of X-ray diffraction, transmission electron microscopy and infrared spectrometry. The tribological behavior of DTC8-Cu as an additive in liquid paraffin was evaluated with a four-ball machine, and the surface topography of the wear scar was also examined by means of scanning electron microscopy. Results show that Cu nanoparticles modified by DTC8 have a small particle size and a narrow size distribution. Besides, DTC8-Cu as an additive in liquid paraffin has excellent antiwear ability, due to the deposition of nano-Cu with low melting point on worn steel surface leading to the formation of a self-repairing protective layer thereon.