Structures, recognition, and some relevant physicochemical properties of small biological molecules, as well as their applications in analysis, are described. The following classes of compounds are discussed: biological ionophores, glycopeptide antibiotics, rifamycins, bile acids and their salts, aminoglycosides, cyclic polypeptide (including thiopeptide) antibiotics, and cinchona and bisbenzylisoquinoline alkaloids. In some cases, interaction of antibiotics with their biological targets is also discussed. Generally, in spite of already several successful practical applications of biological small molecules as receptors, studies on their recognition of analytically important compounds are limited and many biomolecules of appropriate structures have never been tested as receptors yet.