A novel strategy for the synthesis of 2-aroylthienothiazoles via C-H/N-O bond functionalization of ketoximes is developed. This reaction features excellent step- and atom-economy, as well as broad substrate scope. Various common ketoximes, even vinyl ketoximes, were efficiently converted to 2-aroylthienothiazoles. Preliminary mechanistic studies indicated that the radical process should be involved in this transformation. Moreover, the product exhibited good coordination with Cu(II), showing the potential application in the metal coordination field.