Abstract Brazilwood was used in this work to dye wool mordanted with different amounts of copper(II) sulfate, alum and iron(II) sulfate. Two different dyeing methods were used: premordanting (MD) and simultaneous mordanting (M+D) procedures. In order to evaluate the influence of the mordant ion in the brazilein chromophore photodegradation, samples were subjected to artificial light ageing. Color measurements were made and, for the first time, LC-DAD-ESI-MS was used for chromophore analysis of the dyed fibers before and after light exposure. Mordant ion quantification was done after fiber acid digestion, by inductively coupled plasma-optical emission spectroscopy (ICP-OES) and flame atomic absorption spectroscopy (FAAS). Mordant metal ion, mordant bath concentration and dyeing procedure were found to have strong influence in the wool fiber hues. Color variation was more pronounced in the alum dyed samples. Overall, mordant quantification showed that the amount of metal ions found in the fibers is very small when compared to the original concentrations of the dyeing bath, being Cu the ion with greater affinity for the wool fibers. MD dyeing procedure yielded fibers with larger amounts of mordant metal ions and higher chromophore peak areas. Higher amounts of brazilein were extracted from wool mordanted with copper(II) sulfate. Finally, chromatographic analysis of the brazilwood dyed samples before and after light exposure resulted in the detection of Type C compound as an outcome of the photodegradation process.