In conclusion, we have established a general route for forming boron-carbon bonds on dodecaborate clusters, using dihydroxyboryl groups on the carbon moiety. The reaction requires careful consideration of the electron-withdrawing or electron-donating character of the carbon moiety, with a switch of solvent from NMP to CD3CN from electron-withdrawing to electron-donating groups. It tolerates very varied functional groups on the carbon moiety, such as carbonyl, cyano, nitro, and amine, whose reaction could not be achieved previously. This will open up a great number of possibilities for using the exceptional coordination and superchaotropic properties of the dodecaborate cluster.