The molybdacarboranes [3‐{L‐κ2N,N}‐3‐(CO)2‐closo‐3,1,2‐MoC2B9H11] (L=2,2′‐bipyridine (2,2′‐bpy, 1 a) or 1,10‐phenanthroline (1,10‐phen, 1 b)) incorporating well‐known potentially non‐innocent ligands (CO, 2,2′‐bpy, 1,10‐phen) and the “non‐spectator” nido‐carborane ([η5‐C2B9H11]2−) ligand were prepared and fully characterised. High‐resolution mass spectrometry, single‐crystal X‐ray diffraction methods, spectroscopy (IR, (resonance) Raman, NMR), cyclic voltammetry and spectroelectrochemistry (electrochemical properties) were supported by theoretical investigations of the electronic structure (DFT, CAS‐SCF, TD‐DFT).