Seven materials, encompassing a young volcanic soil, its parent material, two older buried soils (Palaeosols), and an underlying older volcanic deposit were investigated in a laboratory study to determine the relationship between dielectric permittivity (ε_c) and water content (θ). Empirical 3rd-order polynomial models generally fitted the data better than semi-physical 3-phase mixing models and normalised conversion functions. Based on their different dielectric response, which presumably is mainly due to their different bulk density (and thus porosity), the materials could be grouped into Ignimbrite materials and Palaeosol materials. Relative to the Ignimbrites, Palaeosols showed a particularly muted response at the low end of dielectric permittivity measurements, which could be due to a particularly high amount of bound water in these allophane-rich materials and/or to greater microstructural and phase configuration effects. Applying the Topp equation resulted in substantial underestimations of the water contents of both groups. A relationship previously developed on New Zealand sandy volcanic soils fitted our Ignimbrite materials well, but still underestimated the water contents of the Palaeosols substantially. Normalised conversion functions described both material groupings reasonably well, demonstrating that bulk density differences can explain a substantial part of the variation of ε_c–θ relationships between different materials.