The combination of catalytic RuCl3 and pyridine with KBrO3 as the stoichiometric oxidant is shown to efficiently promote the hydroxylation of unactivated tertiary C-H bonds. Substrates possessing different polar functional groups - ester, epoxide, sulfone, oxazolidinone, carbamate, and sulfamate - are found to engage in this reaction to give alcohol products in yields generally exceeding 50%. As judged based on efficiency, ease of operation, substrate scope, and selectivity toward tertiary C-H centers, the method appears competitive with other C-H hydroxylation processes.