Colloidal particles with polystyrene (PS) cores and gold nanoparticle (Au NP) coronae were prepared on the basis of the self-assembly of AuNP's and PS. Citrate-stabilized A uNP's were dispersed in aqueous solution, and PS with thiol terminal groups (PS-SH) was dissolved in toluene. A stable emulsion was obtained by mixing the two solutions. Optical microscope images indicate that after grafting of PS-SH to the citrate-stabilized Au NP's at liquid liquid interlace, the interfacial tension is reduced and the average size of toluene droplets in the emulsion decreases. Transmission electron microscope (TEM) results also prove the grafting of PS-SH to AuNP's and the location of the hybrid nanoparticles at the liquid liquid interface. Colloidal particles with PS cores and AuNP coronae were prepared by adding the emulsion to excess methanol. The weight ratio of PS-SH to Au NP exerts a significant effect on the size of colloidal particles. TEM and dynamic light scattering results both indicate that the size of colloidal particles increases with the weight ratio. The application of the core shell-structured colloidal particles to protein separation was also investigated in this research. Colloidal particles with PS-coated magnetic nanoparticles in the cores were also prepared by this strategy.