Many ternary and quaternary semiconductors have been made in nanocrystalline forms for a variety of applications, but we have little understanding of how well their ensemble properties reflect the properties of individual nanocrystals. STROBE researchers at CU Boulder examined electronic structure heterogeneities in nanocrystals of (Ga1−xZnx)(N1−xOx), a semiconductor that splits water under visible illumination. They used valence electron energy loss spectroscopy (VEELS) in a scanning transmission electron microscope to map out electronic spectra of (Ga1−xZnx)(N1−xOx) nanocrystals with a spatial resolution of 8 nm. They examine three samples with varying degrees of intraparticle and interparticle compositional heterogeneity and ensemble optical spectra that range from a single band gap in the visible to two band gaps, one in the visible and one in the UV. The VEELS spectra resemble the ensemble absorption spectra for a sample with a homogeneous elemental distribution and a single band gap and, more interestingly, one with intraparticle compositional heterogeneity and two band gaps. They observe spatial variation in VEELS spectra only with significant interparticle compositional heterogeneity. Hence, they reveal the conditions under which the ensemble spectra reveal the optical properties of individual (Ga1−xZnx)(N1−xOx) particles. More broadly, they illustrate how VEELS can be used to probe electronic heterogeneities in compositionally complex nanoscale semiconductors.