To understand the coordination chemistry of a DO3A-conjugated triphenylphosphonium (TPP) cation, triphenyl(4-((4,7,10-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecan-1 -yl)methyl)benzyl)phosphonium (DO3A-xy-TPP), with diagnostically important metal ions, ln(DO3A-xy-TPP)(+), Ga(DO3A-xy-TPP)(+), and Mn(DO3A-xy-TPP) were prepared by reacting DO3A-xy-TPP with 1 equiv of the respective metal salt. All three complexes have been characterized by elemental analysis, IR, ESI-MS, NMR methods (for ln(DO3A-xy-TPP)(+) and Ga(DO3A-xy-TPP)(+)), and X-ray crystallography. Results from HPLC concordance experiments show that (111)ln(DO3A-xy-TPP)(+) and ln(DO3A-xyTPP)(+) have the same composition. The solid-state structures of ln(DO3A-xy-TPP)(+) and Mn(DO3A-xy-TPP) are very similar with DO3A being heptadentate in bonding to In(III) and Mn(II) in a monocapped octahedral coordination geometry. Because of the smaller size of Ga(III), the DO3A in Ga(DO3A-xy-TPP)(+) is only hexadentate with four amine-N and two carboxylate-O atoms bonding to Ga(III). One carboxylic acid group in DO3A is deprotonated to balance the positive charge of Ga(III). The coordination geometry of Ga(DO3A-xy-TPP)(+) is best described as a distorted octahedron. The NMR data shows that the coordinated DO3A in ln(DO3A-xy-TPP)(+) and Ga(DO3A-xyTPP)(+) is symmetrical in aqueous solution. There is no dissociation of the acetate chelating arms in ln(DO3A-xyTPP)(+) and Ga(DO3A-xy-TPP)(+), providing indirect evidence for the high solution stability of (111)ln(DO3A-xy-TPP)(+) and Ga-68(DO3A-xyJPP)(+).