Worldwide interest in medicinal plants and related drugs is growing because of the increased spectrum of new synthetic drugs. In this context, secondary plant metabolites are most significant. This review analyzes data on the structures and biosyntheses of metabolites such as glycoalkaloids; methods for their extraction from plants of the family Solanaceae, particularly potato S. tuberosum ; their qualitative and quantitative analysis; biological activity; and toxicity. This information could be useful in the selection of methods for sample preparation and extraction of glycoalkaloids during the search for new plant sources with prospects of creating effective and safe pharmacological agents.