The hydrolyzed product of a mixture of tetraethoxysilane (TEOS) and vinyltriethoxysilane (VTEOS) was used to produce organic-inorganic hybrid silica by sol-gel processing. The product was a kind of composite with vinyl groups incorporated into the structure of the final particles through C-Si bonds. These hybrid silica particles were spherical and the average diameter was about 350 nm as measured by scanning electron microscopy (SEM). The particles were non-porous as proved by BET method. The hybrid silica particles were subsequently encapsulated with a layer of PS-DVB, a polymeric mixture of styrene and divinylbenzene, with the vinyl groups on the particle surface as anchors of the polymer chains. The encapsulated packing was used as stationary phases in CEC, and the chromatographic behaviors were studied. Experimental results showed that, as expected, the smaller diameter stationary phase resulted in higher column efficiencies. In comparison with the columns packed with 5 microm diameter encapsulated-silica stationary phases of the same kind and other sub-micron stationary phases reported, it can be concluded that the EOF velocity is independent of the particle diameter when using 350 nm phase, but determined by the surface nature of the stationary phase.