A much improved synthesis for the carbagerma‐closo‐dodecaborate anion [GeCB10H11]– is described in the form of [Bu3NH][GeCB10H11] (1). In reactions with transition metal electrophiles, three transition metal complexes {[Bu3NH][(C6H6)Ru(Cl)2(GeCB10H11)] (2), [Bu3NH][Cp*Ir(Cl)(GeCB10H11)2] (3) and [Me3NH][(PPh3)2Ir(CO)(GeCB10H11)2] (4)} with metal–germanium bonds were synthesized. The carbagermaborate anion, in the form of the salt [Et3NH][GeCB10H11], and the coordination compounds 2–4 were structurally characterized by single‐crystal X‐ray diffraction. Computations were carried out for the anions in 1–4 to aid NMR assignments.

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