A Late Pleistocene/Holocene paleoenvironmental record was obtained from the Rouer peatland (5°54′E, 49°45′N; 270 m a.s.l.), located in the Gutland area of southern Luxembourg. A total of six sediment samples were AMS radiocarbon-dated to obtain an age-depth model. XRF analyses and analyses of geochemical proxies of organic matter (TOC, TN, δ13C, δ15N) were conducted to identify major paleoenvironmental changes in the record. Pollen analysis reveals insights into the vegetation history throughout the last 14,000 cal. yr BP. The record offers unique insights into the evolution of local organic sediment/peat accumulation, as well as into the environmental history of the Gutland region and beyond. The accumulation of organic sediment and peat started at about 13,800 cal. yr BP before present. Until about 6000 cal. yr BP, periods of apparently stable climatic conditions had been interrupted repeatedly by pronounced episodes with increased input of minerogenic matter into the peat matrix (12,700–11,800 cal. yr BP; 11,500–11,300 cal. yr BP; 11,100–10,800 cal. yr BP; 9300 cal. yr BP; 8200 cal. yr BP), indicated by sudden increases of Ti/coh values. After 6000 cal. yr BP, environmental conditions stabilized. Between 4200 and 2800 cal. yr BP, during the Bronze Age, changes in the pollen spectrum indicate an increasing clearance of woodlands. Since the Roman period, an ongoing intensification of grassland farming and agriculture is evidenced. Lowest tree species abundances are witnessed during the Middle Ages. The Modern Era is characterized by enhanced sediment input due to soil erosion. In short, this record complements the Late Pleistocene/Holocene climatic history of the Gutland area and demonstrates that fen peat deposits can be valuable high-resolution paleoclimate archives.