The 1:1 reaction of trans-[(ReCl3)-Cl-III(PPh3)(2)(MeCN)] with 2-(beta-naphthalideneamino)-2-hydroxymethyl-1-propanol, H3L, in toluene gave the dinuclear complex [(Re2Cl4)-Cl-III(HL)(PPh3)]center dot 2C(7)H(8) (1 center dot 2C(7)H(8)), while the 1:2 reaction led to the formation of complex [(ReCl2)-Cl-IV(HL)(PPh3)] (2). In both species, the Schiff-base ligand exists in its doubly deprotonated form, HL2-, forming chelate rings around the metallic centers. In addition, 1 center dot 2C(7)H(8) displays a unique triple metal-to-metal bond between the two trivalent rhenium ions separated at a 2.229(1) angstrom bond distance, while in complex [(ReCl2)-Cl-IV(HL)(PPh3)] (2) the two aromatic ligands, HL2- and PPh3, occupy axial positions, with the terminal Cl- ions in the trans position. Investigation of the magnetic properties revealed a Curie paramagnetic behavior (S = 1/2) with a pronounced temperature independent paramagnetism (TIP) for 1 center dot 2C(7)H(8) and 2. Both the geometry and the electronic structure of both compounds have been studied by means of density functional theory (DFT) calculations, confirming the triplet and doublet spin ground state of the complexes and furthermore establishing an electron-rich sigma(2)pi(4)delta(1)delta*(1) bond order of 3 for 1 center dot 2C(7)H(8). In addition, the absorption spectrum of 1 center dot 2C(7)H(8) in CH2Cl2 was simulated by means of DFT calculations and is in excellent agreement with both the crystallographic and theoretical studies. Complex 1 center dot 2C(7)H(8) is the first dinuclear rhenium complex with a triple metal-metal bond between trivalent rhenium centers.