ABSTRACT This study focuses on the use of micro-sensitive methods – nanoindentation, dynamic water vapour sorption, and X-ray microtomography – to examine the physical properties of small volumes of artists’ materials. The novel methodology proposed in this paper was tested on laboratory-prepared chalk-based ground samples and subsequently applied to distemper paint samples taken from the polychrome walls of Eidsborg stave church. This article discusses key parameters that can be used to inform macro-sized mock-ups mimicking physical and mechanical behaviour of artistic materials, and highlights limitations of such an approach for highly heterogeneous paint systems. Dynamic water vapour sorption measurements allowed determination of the pigment volume concentration (PVC) of distemper paint from Eidsborg stave church as 95%. To the authors’ knowledge, this represents the first assessment of PVC for historic distemper paint using a non-destructive experimental technique, which can be extended to other hygroscopic samples of known composition.