Nitro‐functionalized undecahalogenated closo‐dodecaborates [B₁₂X₁₁(NO₂)]²⁻ were synthesized in high purities and characterized by NMR, IR, and Raman spectroscopy, single crystal X‐diffraction, mass spectrometry, and gas‐phase ion vibrational spectroscopy. The NO₂ substituent leads to an enhanced electronic and electrochemical stability compared to the parent perhalogenated [B₁₂X₁₂]²⁻ (X=F–I) dianions evidenced by photoelectron spectroscopy, cyclic voltammetry, and quantum‐chemical calculations. The stabilizing effect decreases from X=F to X=I. Thermogravimetric measurements of the salts indicate the loss of the nitric oxide radical (NO^.). The homolytic NO^. elimination from the dianion under very soft collisional excitation in gas‐phase ion experiments results in the formation of the radical [B₁₂X₁₁O]^2−.. Theoretical investigations suggest that the loss of NO^. proceeds via the rearrangement product [B₁₂X₁₁(ONO)]²⁻. The O‐bonded nitrosooxy structure is thermodynamically more stable than the N‐bonded nitro structure and its formation by radical recombination of [B₁₂X₁₁O]^2−. and NO^. is demonstrated.