We report the negative ion chemical ionization mass spectra of 2,4-dinitrophenyl (DNP) amino acid methyl esters. For the common amino acids, these derivatives exhibit very simple mass spectra; the molecular anion is the base peak in all cases. The electrophilicity of the DNP group allows selective and sensitive ionization. Amino acids can be identified singly or in mixtures by their molecular weights, and picomole detection is possible. Chromatography is only needed for Leu Ile differentiation. Amino-terminal analysis of proteins is demonstrated.