The synthesis of polyphosphinine macrocycles, which consist of a 16-membered ring with four phosphorus atoms (P4) and a 12-membered ring with three phosphorus atoms (P3), is described. Their high coordination ability is demonstrated by the quantitative synthesis of the rhodium and iridium cation complexes of the P4 macrocycle and by quantitative synthesis of the W(CO)3 complex of the P3 compound. Unlike the other available macrocyclic ligands bearing oxygen, sulfur, di- or tricoordinate nitrogen, and even tricoordinate phosphorus as ligating atoms, which are all essentially final sigma donors, these dicoordinate phosphorus-based macrocycles have strong pi-acceptor properties. Their use can be envisaged for the stabilization of negative oxidation states of transition metals or in reductive catalysis.