Photoluminescence (PL) spectra of the germanium deposited nanostructures grown on silicon (Si) substrate showed a weak UV peaked at 353 nm (similar to 3.4 eV), violet-blue at 402 nm (similar to 3.1 eV), and a broad green band emission in the 470-500 nm (similar to 2.46 eV) range at room temperature when illuminated by 325 nm line laser beam. Electrochemical growth was monitored and evaluated using scanning electron microscopy (SEM), Raman spectroscopy, and PL. SEM images indicated varied current-density-dependent stoichiometry. The origin of the emissions is attributable to GeO2 defect centers, exciton confined in a quantum well, and to unbridged oxygen hole centers. These results perhaps are an indication that the blue luminescence is correlated with the formation of Ge (or GeO2) nanocrystals. The radiative recombinations of excitons confined in the nanocrystals are assessed with a possibility of contributing to the shift in the peak. (C) The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/),which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.