In this paper the potentialities of spectrophotometric and fluorimetric techniques for identifying the materials used in artistic textiles are investigated. A portable non-destructive instrument suitable to record fluorescence spectra on surfaces was set up and successfully experienced. A naturally occurring dye, orcein, which was widely used in antiquity for textile dyeing, has been spectrally characterized in both solution and powder. Laboratory samples of wool and silk orcein-dyed threads were analysed before and after ageing. An original fragment of Renaissance tapestry was also analysed. The textile (wool) and the colourant (orcein) were recognised by comparison with the data from the laboratory samples.