Well-faceted ZnO fibers with periodic junction-prisms were synthesized using conventional chemical vapor deposition. The characterization of the fibers by optical and fluorescence microscopy showed that the outer facets of the crystalline fibers provide excellent mirror-like surfaces for guiding light propagation along the fiber stem as well as the periodic junction-prisms. The structure-related optical properties can be fully explained by a microstructural model. The proposed model explains as the decrease in luminance at the junction-prisms is caused by refraction and total or partial reflection of light. The model also explains the luminance enhancement at the junction-prisms is related to waveguiding of the green emission of the ZnO fibers. Further integration of the ZnO junction-prisms into microdevices should provide the microscale modulation for light with different wavelengths, and could be potentially used for enhanced light-illumination arrays.