In this thesis, textiles from various periods and regions have been investigated to determine the kind of fibers and colorants having been used. The results obtained give some clues concerning the used raw materials and dyeing technologies. Furthermore, the results can help to develop strategies for conservation and restoration of such historical objects. A central issue was the first-time application of ambient MS techniques, such as ASAP-MS or flowprobe-ESI-HRMS, for dyestuff analyses on historical textiles. These techniques enable minimally invasive analyses of dyestuffs directly from the surface of fiber samples. The identification of dyestuffs was largely independent of sample properties and fiber material. These methods require no time-consuming sample preparation and experiments were completed within a few minutes or seconds. In addition, spatially resolved dyestuff analyses of multicolored, textile fabrics were performed by mass spectrometry imaging. The investigations focused on the detection of anthraquinones and indigo-type dyes.