To better understand the influence of microscale geochemical and microstructural relationships on the bulk petrophysical properties of unconventional shale systems, core samples from four producing North American formations were cross-sectioned with an argon ion polisher and imaged with a field emission scanning electron microscope (FE-SEM) using a variety of complementary detectors. We demonstrate distinct advantages of the ion-polishing technique for the preservation of the internal shale structure. Moreover, we show how such preparation affords a wider choice of imaging options for both chemical and structural characterization, such as backscatter electron observation at varying beam potentials coupled with x-ray and cathodoluminescence spectroscopic techniques.