Carborynes can exist in two resonance forms, bonding form vs biradical form. The biradical form can be readily generated via the elimination of LiI from 1-iodo-n-lithio-1,n-C(2)B(10)H(10) (n = 2, 7) under UV irradiation. They can undergo alpha-C H bond insertion with aliphatic ethers, affording alpha-carboranylated ethers in excellent regioselectivity at room temperature. This serves as a new methodology for the generation of a series of functionalized carboranes bearing alkoxy units.