28,000 chiral compounds separated by chiral chromatography have been selected in ChirBase database. The enantiomers of this library can be considered as potentially being isolable by chromatography at a small-scale level of development. The resulting chiral pool was analysed with the aim to describe compound molecular diversity as well as druglike and lead-like characteristics. In parallel, we have explored the possibility of using this chiral product library as starting materials for the construction of a virtual chiral combinatorial library. The chemical space occupied by the obtained combinatorial collection of new chiral scaffolds revealed that structures of the chromatographic-based chiral library may also be a source of chiral diversity for drug discovery. Another interesting in silico approach consisted to release all the protected or derivatized compounds. This procedure allowed us to enrich and expand the existing library with several thousands of original small chiral amines, acids and alcohols. Finally, sub-similarity searching strategies were found valuable for quickly selecting suitable small chiral precursors that are readily available from chiral chromatography for the small-scale synthesis of some known chiral drugs.