A one-pot procedure has been developed for the synthesis of 3-aroyl-2-(polyfluoroalkyl)quinoxalines and 3-aroyl-2-(polyfluoroalkyl)benzo[g]quinoxalines by nitrosation of lithium 3-(polyfluoroalkyl)-1,3-diketonates and subsequent reaction with benzene-1,2-diamine or naphthalene-2,3-diamine, respectively.