Dirhodium(II) caprolactamate (1), Rh₂(cap)₄, is a highly effective catalyst for C-H oxidation when paired with t-butyl hydroperoxide (t-BuOOH). Using this catalytic system, allylic, benzylic, and secondary amine oxidations have been reported. For this work, alternate reaction conditions, including the use of water as an �environmentally friendly' solvent, are explored. Consequently, the scope of C-H oxidation can be expanded to include propargylic substrates to form α,β-acetylenic carbonyl compounds. Most reactions are performed at ambient temperature and all employ an inexpensive and easy to handle oxidant, T-HYDRO^� (70% t-BuOOH in water). The breadth of propargylic oxidation and synthetic applications of α,β-acetylenic ketones are also reported.