Tridentate and tetradentate polyphosphines offer a huge variety of coordination modes to transition metals which lead, depending on the metal, to very different structural features in the resulting complexes. Steric effects being crucial in metal–phosphine complexes reactivity, a good knowledge of the molecular structures of the species is required both in the solid state and in solution. This article reviews from a structural point of view the monometallic and symmetrical homobimetallic complexes of the transition elements of Group 6 to 10 with tridentate and tetradentate phosphines. Concerning the classical triphosphines and tetraphosphines, emphasis was put on advances reported after the year 1994, since comprehensive reviews have covered the former period. Several anterior relevant results are, however, briefly mentioned when necessary. A second part is devoted to nitrogen- and sulfur-containing derivatives potentially tridentate and tetradentate ligands, and their coordination to the above-mentioned metals. The last part describes the complexes obtained with the less classical ferrocenyl polyphosphine ligands or their nitrogen-containing derivatives: each ligand having a potential tridentate or tetradentate coordination from either phosphorus or nitrogen donor atoms. The literature cutoff date was during the second half of 2000, but in a few cases, references to important work appearing during 2001 were made; however such coverage should be completed in a future compilation. An exhaustive quoting of catalytic applications and reaction chemistry was beyond the scope of this article mainly devoted to structural works. Nevertheless, in order to illustrate the importance of this chemistry, efforts were made to provide the reader with recent references that have marked the field, even in the absence of X-ray structural characterization.