Three investigations were conducted in this article-style dissertation, all sharing the common goal of achieving improved characterization of geopolymers in a manner that provides nanostructural information. The first study revisited the use of statistical nanoindentation for characterizing the micromechanical properties of heterogeneous materials and explores the limitations of the method for future applications with geopolymers. In the second investigation, a novel method was developed for quantitatively analyzing the microsturcture of geopolymers by using electrical resistivity measurements. The method was found to provide insight into the nanoscale porosity. The third investigation utilized atom probe tomography (APT) to observe the effect of elevated temperature of the nanostructure of a fly ash geopolymer. Complimentary analysis techniques from the first two investigations were used to support the findings from APT. The outcomes of this dissertation are additional insight into the nanostructure of geopolymers, as well as several new characterization tools that may see broader use for other cementitious materials in future research.