In this paper, hexagonal germanium dioxide (GeO2) nanostructures with different morphologies and sizes were synthesized successfully by a simple and fast electrodeposition method. We investigated the electrochemical growth mechanism, the structural and optical properties of the products through Fourier transform infrared spectroscopy (FTIR), dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and cathodoluminescence (CL). The results reveal that the electrodeposited GeO2 nanostructures are pure, dense, and highly crystalline. The XRD analyses indicate that grown GeO2 crystals only shows peaks related to α-quartz structure. CL measurements exhibit strong blue and green lights emissions related to oxygen vacancies in the core of GeO2 crystals. The obtained nanostructures may have potential application in future integrated optical devices.