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We have performed Co K-edge x-ray absorption fine structure and x-ray absorption near edge structure measurements of Co-doped plasma enhanced chemical vapor phase deposition (PECVD) grown “C2B10Hx” semiconducting boron carbides, using cobaltocene. Cobalt does not dope PECVD grown boron carbides as a random fragment of the cobaltocene source gas. The Co atoms are fivefold boron coordinated (R=2.10±0.02 Å) and are chemically bonded to the icosahedral cages of B10CHx or B9C2Hy. Pairwise Co doping occurs, with the cobalt atoms favoring sites some 5.28±0.02 Å apart.