The purpose of this study was to investigate the formation mechanism of colloidal nanoparticles after dispersion of probucol/polyvinylpyrrolidone (PVP)/sodium dodecyl sulphate (SDS) ternary ground mixture (GM) into water. Probucol, PVP and SDS were mixed at a weight ratio of 1:3:1 and ground for 30 min with a vibrational rod mill. The morphology and physicochemical properties were investigated through high resolution scanning electron microscopy (SEM), environmental SEM, dynamic light scattering, 13C NMR and zeta potential measurements. SEM images confirmed the presence of 20 nm size primary particles in the GM powder of probucol/PVP K17/SDS. Spherical nanoparticles with a size of around 100 nm, formed after dispersion of the GM into water, suggested an agglomeration of the primary particles. A further agglomeration of around 160 nm was observed with the stability experiment. Zeta potential and particle size measurements using latex beads revealed that PVPK 17/SDS complex was adsorbed on the probucol particle surface forming a layered structure. A similar agglomeration behavior was observed using the GM of probucol/PVP K12/SDS, though the molecular state of the PVPK 12/SDS complex at the particle surface was different from that of the PVPK 17/SDS complex. 13C NMR results suggested that intermolecular interactions between PVP K12 and SDS did not reach the same level as the interactions between PVP K17 and SDS. This study proposed a formation mechanism of colloidal nanoparticles.