The polycrystalline Cu (In, Ga) Se2, or CIGS, based thin-film materials system has long been studied for use in photovoltaic technologies, where its bandgap tunability, mechanical flexibility, and relatively low production costs are all appealing. Nonetheless, significant defect populations, which serve to reduce efficiency, create performance instabilities, and increase concerns about long-term reliability, have hindered wide-scale adoption. Prior work, including application of a scanning probe based deep level trap spectroscopy (SP-DLTS) defect mapping technique and scanning transmission electron microscope (STEM) based electron energy loss spectroscopy (EELS), has shown that the most detrimental defects, with energy level near mid-gap (thus serving as a carrier recombination center), are most likely caused by CuIn/Ga antisites and tend to cluster at or around certain grain boundaries [1,2]. However, the exact nature of these particular boundariestheir structures, chemistries, or even the relative misorientation of their associated grainsand their relation to this defect clustering and/or its formation is yet unknown. As such, electron backscatter diffraction (EBSD) orientation mapping, directly correlated with defectsensitive techniques like SP-DLTS and/or STEM-EELS, could prove critical for providing the final missing links toward understanding the mechanisms behind these defects. Indeed, recent studies using correlative electron beam induced current (EBIC) with EBSD have been able to identify boundaries, and their relative misorientations, that possess detrimental electronic properties [3]. However, because EBIC is unable to resolve the defect energy levels, many questions are left unanswered. Furthermore, this study, and others like it, employed focused ion beam (FIB) milling to flatten the natively-rough CIGS [3-5], which may run the risk of changing the nature of any near-surface defect structures.