This manuscript provided one of the first scientific studies performed on ancient Spanish liturgical vestments by using a multitechnical physicochemical approach. The interlining and lining fabrics were done by cotton and the core of threads by silk. Silver, gold and little amounts of copper were detected. The highest values of gold were found in the metal threads of the cope and the gallon of the chasuble. Two layers were identified: the internal composed by silver and the external by silver and gold. The fibers were proved to be degraded and also the surface of the metal, where scratches and silver-based compounds were detected due to environmental and anthropogenic actions. Indigo was employed as dye in the blue and green fabrics. Wax was detected in the yellow fibers, although other dyes could not be discarded. The materials used in the restoration processes were of minor quality.