Abstract An atom‐economical method for the direct B−H functionalization of nido ‐carboranes (7,8‐ nido ‐C 2 B 9 H 12 − ) has been developed under electrochemical reaction conditions. In this reaction system, anodic oxidation serves as a green alternative for traditional chemical oxidants in the oxidation of nido ‐carboranes. No transition‐metal catalyst is required and different heteroatoms bearing a lone pair are reactive in this transformation. Coupling nido ‐carboranes with thioethers, selenides, tellurides, N‐heterocycles, phosphates, phosphines, arsenides and antimonides demonstrates high site‐selectivity and efficiency. Importantly, nido ‐carboranes can be easily incorporated into drug motifs through this reaction protocol.