Biocodicological analysis of parchments from manuscript books and archives offers unprecedented insight into the materiality of medieval literacy. Using ZooMS for animal species identification, we explored almost the entire library and all the preserved single leaf charters of a single medieval Cistercian monastery (Orval Abbey, Belgium). Systematic non-invasive sampling of parchment collagen was performed on every charter and on the first bifolium from every quire of the 118 codicological units composing the books (1490 samples in total). Within the genuine production of the Orval scriptorium (26 units), a balanced use of calfskin (47.1%) and sheepskin (48.5%) was observed, whereas calfskin was less frequent (24.3%) in externally produced units acquired by the monastery (92 units). Calfskin was preferably used for higher quality manuscripts while sheepskin tends to be the standard choice for ‘ordinary’ manuscript book production. This finding is consistent with thirteenth-century parchment accounts from Beaulieu Abbey (England) where calfskin supply was more limited and its price higher. Our study reveals that the making of archival documents does not follow the same pattern as the production of library books. Although the five earliest preserved charters are made of calfskin, from the 1230s onwards, all charters from Orval are written on sheepskin.