Besides being a versatile entity for further chemical transformations, the propargylic subunit is also part of various natural products, fine chemicals, and synthetic pharmaceuticals. Propargylic substitution reactions, however, are rather unexplored. An overview of this emerging field is presented. We especially focus on experimental results that deal with catalyzed substitutions of propargylic alcohols and their derivatives. Finally, some enantioselective propargylic substitution methods are discussed. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)