Methylcarbamate insecticides react rapidly and quantitatively with trifluoroacetic (TFA), pentafluoropropionic (PFP), and heptafluorobutyric (HFB) anhydrides to give jV-perfluoroacylated derivatives. Unlike many of the parent methylcarbamates, the derivatives are stable to gas chromatographic conditions and detected at low levels by the electron-capture and alkali-flame ionization detectors. The infrared, nmr, and mass spectral properties of the compounds are characteristic and permit ready qualitative identification. The applicability of trifluoroacetylation to eight methylcarbamate insecticides and the metabolites of carbofuran was demonstrated.