In Western Europe, most of the oldest prehistoric sites (ranging from 2 Ma to 500 ka) are associated with clastic or carbonated karstic environments. Here, the electron spin resonance (ESR) dating method is often the only one method permitting to place these localities in the global Quaternary framework, which is mainly based on marine isotopic data and palaeomagnetical record. ESR can be applied on different materials frequently recovered in archaeological sites such as tooth enamel, quartz grains or carbonates. In this paper, we present the results, which have been obtained for more than ten years on different archaeological sites of the late Lower Pleistocene or the early Middle Pleistocene, which are crucial for the understanding of the first human settlements of Europe: Pont-de-Lavaud and Grâce-Autoroute (France), Atapuerca Gran Dolina (Spain), Monte Poggiolo and Isernia La Pineta (Italy). Wherever possible, the ESR results were compared with those of independent dating methods, including 39Ar/40Ar, palaeomagnetism and biostratigraphy. In some cases, the ESR method applied on bleached quartz extracted from fluvial sediments and the ESR /U-series method on tooth enamel were the only available methods to provide geochronological data.