Earth-abundant and environmentally friendly semiconductors offer a promising path toward low-cost mass production of solar cells. A critical aspect in exploring new semiconducting materials and demonstrating their enhanced functionality consists in disentangling them from the artifacts of defects. Nanowires are diameter-tailored filamentary structures that tend to be defect-free and thus ideal model systems for a given material. Here, an additional advantage is demostrated, which is the determination of the band structure, by performing high energy and spatial resolution electron energy-loss spectroscopy in aloof and inner beam geometry in a scanning transmission electron microscope. The experimental results are complemented by spectroscopic ellipsometry and are excellently correlated with first principles calculations. This study opens the path for characterizing the band structure of new compounds in a non-destructive and prompt manner, strengthening the route of new materials discovery.