In this work, the surface of hydrophilic cellulose nanofibrils (CNFs) was modified precisely by varying amounts of cetyltrimethylammonium bromide (CTAB) to produce CNF-based particle surfactants. We found that a critical CTAB density was required to generate amphiphilic CTAB-grafted CNF (CNF-CTAB). Compared to pristine CNF, CNF-CTAB was highly efficient at stabilizing oil-in-water Pickering emulsions. To evaluate their effectiveness as particle surfactants, the surface coverage of oil-in-water emulsion droplets was determined by changing the CNF-CTAB concentration in the aqueous phase. Furthermore, styrene-in-water stabilized by CNF-CTAB surfactants was thermally polymerized to produce CNF-stabilized polystyrene (PS) particles, offering a great potential for various applications including pharmaceuticals, cosmetics, and petrochemicals.