All modern day materials have to be characterized in order to understand their properties. Simple techniques can be used for macrostructural and microstructural characterization. Many a time, however, advanced techniques may be required in order to understand structure property relationships in a better way. Advanced characterization techniques include scanning electron microscope (SEM), transmission electron microscope TEM, nuclear magnetic resonance (NMR), synchrotron, X-ray fluorescence microscopy and a few others. Geopolymers have advanced to the level of nanogeopolymers, and in order to understand the fundamental properties of nanogeopolymers, it becomes imperative to gain a fundamental understanding of characterization methods. SEM, TEM, NMR and synchrotrons have been briefly described, and advances in these characterization techniques have been emphasized. Microstructures of common geopolymers have been discussed with special emphasis on nanogeopolymers.