The compound [Rh₁₄C₂(µ-CO)₂₁(CO)₁₂]^2– has been synthesized by reaction of [Rh₆C(CO)₁₅]^2– with [Rh(CO)₂(MeCN)₂]⁺. Its molecular structure has been determined by single-crystal X-ray crystallography: monoclinic, space group C_2/m, with a= 13.496(1), b= 37.175(2), c= 15.858(1)Å, β= 113.9(1)°, and Z= 4. The structure has been solved from 3 460 reflections collected by counter methods and refined by least-squares calculations to R= 0.042. The dianion has idealized D_3h symmetry and contains two Rh₇C moieties related by a crystallographic mirror plane. Each unit is a C_3v monocapped trigonal prism. The two halves are linked by a Rh–Rh bond between the capping atoms and by three bridging carbonyl ligands. The remaining 30 CO groups are distributed 15 on each Rh₆ prism, the geometry of the parent [Rh₆C(CO)₁₅]^2– anion being retained. The Rh–Rh bond between the two Rh₇ units is remarkably short, 2.570(2)Å. Other relevant (average) bond distances are as follows: Rh–Rh 2.778, Rh–C(carbide) 2.14; Rh–C and C–O for terminal and bridging ligands 1.89 and 1.14 and 2.07 and 1.17 Å, respectively. A comparison is made with the clusters [Rh₈C(CO)₁₉], [Cu₂Rh₆C(CO)₁₅(MeCN)₂], and [Ag{Rh₆C(CO)₁₅}₂]^3–.