Preparation of nano-CdS particles with surface thiol modification by microemulsion method and their influences on the particle size distribution in highly filled polystyrene-based composites were studied. The modified nano-CdS was characterized by X-ray photoelectron spectroscopy (XPS), light absorption and emission measurements to reveal the morphologies of the surface modifier, which are consistent with the surface molecules packing calculation. The morphologies of the surface modifier exerted a great influence not only on the optical performance of the particles themselves, but also on the size distribution of the particle in polystyrene matrix. A monolayer coverage with tightly packed thiol molecules was believed to be most effective in promoting a uniform particle size distribution and eliminating the surface defects that cause radiationless recombination. Control of the particles size distribution in polystyrene can be attained by adjusting surface coverage status of the thiol molecules based on the strong interaction between the surface modifier and the matrix.