Chirality is vital in chemistry. Its importance in atomic clusters has been recognized since the discovery of the first chiral fullerene, the D2 symmetric C76.1 A number of gold clusters have been found to be chiral,2 raising the possibility to use them as asymmetric catalysts. The discovery of clusters with enantiomeric structures is essential to design new chiral materials with tailored chemical and physical properties.3 Herein we report the first inherently chiral boron cluster of B30− in a joint photoelectron spectroscopy and theoretical study. The most stable structure of B30− is found to be quasiplanar with a hexagonal hole. Interestingly, a pair of enantiomers arising from different positions of the hexagonal hole are found to be degenerate in our global minimum searches and both should co‐exist experimentally because they have identical electronic structures and give rise to identical simulated photoelectron spectra. Holey chiral: The B30− cluster was characterized by photoelectron spectroscopy and ab initio calculations. A pair of planar structures with a hexagonal hole at different positions are found to be degenerate with identical electronic structures. These two isomers are enantiomers, suggesting that B30− is the first chiral boron cluster.