Neolithic occupation of the Orkney Islands, in the north of Scotland, probably began in the mid fourth millennium cal BC, culminating in a range of settlements, including stone-built houses, varied stone-built tombs and two noteworthy stone circles. The environmental and landscape context of the spectacular archaeology, however, remains poorly understood. We applied the Multiple Scenario Approach (MSA) to Neolithic pollen records from Mainland, Orkney, in order to understand land cover and landscape openness across the timespan 4200–2200 cal BC. Interpreted within a framework provided by Bayesian chronological modelling, 406 radiocarbon dates from archaeological contexts and a further 103 from palaeoenvironmental samples provide the basis for the first detailed reconstruction of the spatio-temporal patterns of Neolithic people and their environment. Major alterations to the land cover of Mainland took place from 3400 cal BC (reduction in woodland from 20% to 10%) and from 3200 cal BC (increase in disturbed land from 3% to 30%). The dramatic increase in disturbed land coincided with the Grooved Ware phenomenon and the establishment of settlements at Skara Brae and Ness of Brodgar. The upturn in the signal for disturbance communities in the pollen record may indicate an increase in the amount of land used as pasture. This accords with the archaeological record, since the Neolithic Orcadian economy probably relied heavily on cattle for subsistence. By 2800 cal BC in the core of the Orkney Mainland, most settlements appear to have been ending, with people dispersing into the wider landscape, as the MSA modelling indicates a maintenance of disturbed land, and indeed a subsequent slight increase, implying persistence of human activity elsewhere in Mainland. People exhausted themselves rather than their land; that and its varied resources endured, while the intensive social relationships and practices of the peak of late Neolithic Orkney could not be maintained.