Electrocatalyzed oxidative B−H nitrogenations of nido-carborane (nido-7,8-C2B9H12−) with N-heterocycles have been established, enabling the preparation of various N-substituted nido-carboranes without chemical oxidants or metal catalyst under ambient conditions. The electrolysis manifold occurred with high levels of efficiency as well as chemo- and position- selectivity, employing sustainable electricity as the sole oxidant. The strategy set the stage for a user-friendly access to novel amino acid and fluorogenic boron-dipyrrin (BODIPY)-labeled nido-carborane hybrids. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH