Photoelectron spectroscopy and quantum chemistry studies are used to investigate the structure and bonding of AuB8-. Global minimum sturctural searches show that AuB8- possesses a chair-like structure, which can be viewed as Au+ bonded to the edge of the doubly-aromatic B82- borozene, Au+[η2-B82-]. Chemical bonding analyses reveal that the AuB8- is a novel borozene complex with unique Au-borozene bonding.