X-ray fluorescence spectrometry (XRFS) was used in the analysis of A horizon soil samples collected from a former farming settlement and its associated area of infield (i.e. arable) located in the Central Highlands of Scotland. To date, XRFS has not been extensively used in geoarchaeological research, but in our study the simultaneous multi-element capabilities of this instrumental technique allowed the total concentrations of 25 major, minor, and trace elements to be fully quantified with acceptable levels of accuracy and precision. Included within this group of chemical elements are a number (e.g. Ba, Ca, P, Pb, Sr and Zn) that have proved to be of value to archaeological interpretation in earlier investigations undertaken in Scotland. In our preliminary work documented here, significant differences were found between the A horizon soils of former settlement and infield areas for 18 chemical elements. Subjecting the XRFS data—and three other measured variables: soil organic carbon (SOC), pH and A horizon depth—to discriminant analysis indicates that soils of former settlement and arable farming can be effectively classified according to their pH, SOC content and Ca, Cu, Mg, Rb, and Zn concentrations. The inference is that areas of former infield and settlement elsewhere at this study location in the Central Highlands may be able to be identified according to their soil chemical composition and use of discriminant function, even though the surface remains of pre-eighteenth century settlement sites are not readily evident today because they were constructed of perishable materials.