The syntheses of several tripodal phosphinine-based ligands are presented. 1,3,2-Diazaphosphinine (1) undergoes Diels−Alder reactions with tris-(propynyl)phenylsilane to yield tris-(1,2-azaphosphinine)phenylsilane 6. This intermediate serves as precursor for the preparation of two tripodal ligand. First, tris(phosphinine)phenylsilane (7) is obtained from the reaction with trimethylsilylacetylene. Under more drastic conditions, compound 6 reacts with 4-octyne to yield the tripodal ligand 8 containing six n-propyl groups. Reaction of 8 with [W(CO)5(THF)] affords the corresponding W(CO)3 complex 9 whose structure was confirmed by an X-ray crystallographic study. The synthesis of two extended tripodal ligands 12 and 13 containing three phosphinine units each connected to the same CH linker by dimethylsilyl groups was also studied. As a prerequisite, the precursor tris(propynyldimethylsilyl)methane (10) was synthesized by reaction of three equivalents of propynyllithium with tris(bromodimethylsilyl)methane. Reaction of excess 1 with 10 yielded the corresponding tris(dimethylsilyl-1,2-azaphosphinine)methane (11) as an intermediate. The formation of ligands 12 and 13 was achieved by reacting 11 with trimethylsilylacetylene or 4-octyne, respectively, in excess. The reaction of ligand 13 with [W(CO)5(THF)] in toluene yielded the corresponding W(CO)3 complex 14 which was structurally characterized.