The structures and bonding of GB(6)(-), C2B5-, and CB62- are investigated by photoelectron spectroscopy and ab initio calculations. It is shown that the global minimum structures for these systems are distorted heptacyclic structures. The previously reported hexacyclic structures with a hypercoordinate central carbon atom are found to be significantly higher in energy and were not populated under current experimental conditions. The reasons why carbon avoids hypercoordination in these planar carbon-boron clusters are explained through detailed chemical-bonding analyses.