Onion-like carbon (OLC) is a kind of carbon material with a graphene-like structure and large interlayer spacing, favorable to a good lubricating performance. Herein, a facile method is presented for the preparation of functionalized OLC nanoparticles from candle soot with surface modification. The OLC nanoparticles are collected from combustion soot with candle burning via a simple heat treatment, and then the zwitterionic polymer (polyethylenimine-quaternized derivative, PEIS) can self-assemble onto the OLC surface with epigallocatechin gallate via Michael addition and Schiff-base reaction, thus obtaining PEIS-functionalized OLC nanoparticles (PEIS@OLC). The grafting zwitterionic polymer PEIS endows the OLC nanoparticles with good hydrophilic performance, so the as-obtained PEIS@OLC exhibits outstanding dispersion and lubricating property as a water-based lubricant additive. Compared to pure water, the average coefficient of friction decreases to 0.110 from 0.512, and the corresponding wear volume is reduced by 61.02% with 1.5 wt % addition. The improved lubricating property is mainly due to the synergetic effect of the protective film induced by the tribochemical reaction and the hydration film of zwitterionic polymer PEIS. Besides, the OLC nanoparticles could also display the nanoscale rolling and repairing effects at the friction contact interface, resulting in reduction of friction and wear.