The closo‐hydro‐borate [B6H6]2– reacts with DBU (= 1,8‐Diazabicyclo[5.4.0]undec‐7‐en) in chloroform to give a mixture of two different seven‐vertex monocarboranes, 3‐DBU‐closo‐2‐CB6H6 and [3‐Cl‐closo‐2‐CB6H6]–. Dichlorocarbene, which is generated in situ by the reaction of DBU with chloroform at elevated temperatures, subsequently inserts into the [B6H6]‐closo‐cluster to result in 3‐DBU‐closo‐2‐CB6H6 as main product [3‐Cl‐closo‐2‐CB6H6]– was obtained as a byproduct. Both novel carboranes were isolated and characterized by 1H, 1H{11B}, 11B, 11B{1H} and 13C NMR spectroscopy. The structures of 3‐DBU‐closo‐2‐CB6H6 as well as [3‐Cl‐closo‐2‐CB6H6]– were determined by single‐crystal X‐ray diffraction.