The production of nanostructured bulk materials from silicon powders has been well documented as being one way of bringing down the thermal conductivity of silicon while still maintaining its high power factor. This reduction of thermal conductivity is predicted to lead to significant increases in its figure-of-merit, ZT. The size of the starting particles has a major effect on the nanostructuring and grain size of the final silicon-based materials. Using particles of differing size and distribution, pellets were produced using spark plasma sintering. The results show a significant lowering in the thermal diffusivity as the particle size in the powders is decreased. As the starting particle size deceases from 1 μm to 60 nm, we see a tenfold decrease in the thermal diffusivity at 300 K, from 20 mm2 S−1 to 2 mm2 S−1. Both these show a significant decrease from the thermal diffusivity of 88 mm2 S−1 observed from bulk silicon. A further decrease to 1 mm2 S−1 is observed when the particle size of the starting material is decreased from 60 nm to sub-10 nm. The results also highlight the potential of using particles from solution approaches as a potential starting point for the prediction of nanostructured bulk materials.