a b s t r a c tPhosphines are one of the most important classes of ligands in chemistry, in both the industrial and academic spheres. This review deals with the design and properties of polydentate phosphines, an original and broad class of multidentate ligands. The multidentate nature of these species has led to special properties, in which the spatial proximity of phosphorus atoms is crucial. The first part gives an overview of oligodentates polyphosphines in which is discussed the types and the basic routes for their synthesis. The review continues with the most important synthetic routes for obtaining complexes. Because of huge amount of literature data this review is not exhaustive, but it collects the most relevant findings in this area. The restriction to structural and spectroscopic properties allows us for a well organized handling of the complex material.