Within archaeological studies of ancient pottery, understanding the techniques used to form vessels from unfired clay provides significant information on the history of technology and economic systems, as well as wider cultural practices and social interactions. We introduce here a new analytical methodology, using small-angle neutron scattering (SANS) to investigate pottery forming techniques through the preferential orientation of nanoscale objects within pottery fabrics. Significantly, SANS is non-destructive, suitable for both coarse and fine-textured pottery fabrics, provides quantitative data, enables fast-throughput of samples, and is not significantly affected by surface modifications occurring after the primary forming stage. The use of SANS is systematically investigated through over 400 measurements of experimental vessels, and also compared with X-ray microtomography and neutron tomography. The results show that SANS can be used to differentiate wheel-throwing, coil-building, percussion-building, and coil-wheeling techniques. The archaeological application of SANS is demonstrated through a case study of 50 late Roman and early medieval (fourth–sixth century AD) pottery sherds from Hungary, spanning the collapse of the Western Roman Empire and the arrival of Barbarian polities into the region. The findings show a transition in production from predominantly wheel-throwing to coil-wheeling, but also coil-building, percussion-building, percussion-wheeling, and drawing. Such changes appear to reflect the disintegration of large-scale centrally organised Roman economic systems, and the diversification of production, consistent with the more diversified technological and cultural backgrounds of the producers themselves.