Among the different types of metal oxides, zinc oxide (ZnO) is a most commonly used metal oxide in a broad variety of applications. In the present investigation, a modified green synthesis route was used to synthesize pure and starch-capped ZnO (ZnO/starch) quantum dots (QDs) and studied their structural and optical characteristics. In this study, hexagonal crystal structure was observed in both pure and ZnO/starch QDs using X-ray diffraction technique. A spherical-shaped surface morphology was found with the size of 5-10 nm using transmission electron microscope technique. The interaction between ZnO QDs and starch molecules was proved via Fourier infra-red spectrometer technique. On the other hand, their fluorescence behaviors were investigated using photoluminescence technique, in that the ZnO/starch QDs showed an enhanced emission behavior when compared to the pure ZnO QDs. Further, the solar photocatalytic activity of both the ZnO QDs was examined with the dye Rhodamine B (RhB) at the end of 30, 60, 90, and 120 min. In this, ZnO/ starch QDs show a good and more decomposition of RhB than pure ZnO QDs. Collectively, in the present study, green synthesis route produced an efficient QDs (pure and ZnO/starch) and it will be very useful for many other QDs. The ZnO/starch QDs are suitable for decomposing the RhB and other toxic organic dyes.