Polysaccharide-based chiral selectors are in wide use in chiral chromatography, both in the analysis and in the purification of chiral compounds. The use of superficially porous silica (SPS) particles, proven successful in various modes of liquid chromatography, is an obvious opportunity to elevate the performance of polysaccharide-based chiral stationary phases as well. In this chapter, the preparation, characterization, and chromatographic evaluation of chiral stationary phases made by combining superficially porous silica with polysaccharide-based chiral selectors are described.