Dyestuff analyses were performed directly from the surface of different bluish and reddish colored historic textile samples by flowprobe™-electrospray ionization-high-resolution mass spectrometry (flowprobe™-ESI-HRMS). This real-time in situ microextraction method allowed rapid, reliable and minimal-destructive analysis without extra and time-consuming sample preparation and required only a minimum amount of valuable archaeological material. As demonstrated for indigo-type and anthraquinone dyes this technique is useful for the analysis of various types of textiles regardless of their fiber matrix, appearance or handicraft and is also suitable for investigating fragile archeological fibers. Thus, flowprobe™-ESI-HRMS is a promising analytical tool for characterizing organic colorants in objects of archaeological interest.