This paper outlines techniques that have been developed or adapted to characterise the internal structure of gibbsite agglomerates and their application to selected laboratory gibbsite sample. The specific structural properties investigated include the quantification of gibbsite voidage (Floc Density Analyser), determination of relative changes in gibbsite crystal orientation (Raman spectroscopy and electron backscattered diffraction) and location of the cement binding agglomerated gibbsite particles (Raman spectroscopy, charge contrast and orientation contrast imaging). This paper also describes the use of Kikuchi patterns for investigating crystal orientation at a point and as a tool to assess if a particle is a single crystal or an agglomerate or a multi-fold twin.