The identification of the colorants used on ancient textiles provides a historical pathway to the understanding of the processes associated with one of the oldest of chemical technologies, namely textile dyeing. In this paper, time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used to detect dyes on textiles avoiding the time-consuming and destructive extraction procedures necessary for the spectrophotometric and chromatographic methods previously used. The plant dyes investigated belong to a variety of chemical groups, which include curcumin, crocin, carthamin, purpurin, alizarin, brazilin, shikonin, and indigo. Reference textile samples were prepared with dye extracts of plants and were characterized by TOF-SIMS. TOF-SIMS spectra for the dyed textiles showed element ions from metallic mordants, specific fragment ions, and molecular ions from organic dyes. Remnant dyes on excavated textiles have also been identified using TOF-SIMS. The ancient textile sample showed the presence of indigo clearly, although the fiber itself had degraded badly. From the results, it was concluded that most of plant dyes can be identified with TOF-SIMS and it is a very promising technique for the archaeology field. (C) 2008 Elsevier B. V. All rights reserved.