Textile production is among the most fundamental and more complex technologies in human prehistory, but is under-investigated due to the perishable nature of fibrous materials. Here we report a discovery of five textile fragments from a prehistoric (fourth-third millennium cal BC) burial deposit located in a small cave at Penacalera in Sierra Morena hills, near Cordoba, Southern Spain. These textiles accompanied a set of human remains as grave goods, together with other organic elements such as fragments of wood and cork, and some pottery vessels. They were characterized and dated using digital microscopy, Scanning Electron Microscopy, Energy Dispersive Spectroscopy and Accelerator Mass Spectrometry. Two of the fragments described here are the oldest examples of loom-woven textiles in the Iberian Peninsula, dating from the second half of the fourth millennium cal BC. This correlates chronologically with the first appearance of loom weights in the archaeological record of this region. The more recently dated textile is the earliest preserved cloth intentionally coloured with cinnabar in the western Mediterranean. The Penacalera finds are a key reference for understanding the development of textile technologies during the Neolithic and Copper Age in western Europe and beyond.