Recently we reported our results on the successful synthesis of 3-D highly ordered macroporous (3DOM) structure of germanium via the template-assisted electrochemical deposition from air- and water stable ionic liquids. Herein we report our new results on the photoluminescence (PL) properties of the obtained ordered macroporous Ge and the Ge/polystyrene composite opal structure. The latter showed a strong green emission compared to a Ge film and a Ge inverse opal. The enhancement of PL intensity was ascribed to the disorder multiple scattering in polystyrene colloidal crystal structure which increased both the excitation light absorption efficiency and the light extraction efficiency. The X-ray photoelectron spectroscopy (XPS) results suggested that the ordered macroporous Ge was capped with an oxide layer including a considerable amount of GeO(2). The observed green emission (539 nm) was related to GeO(2), likely resulting from the Ge-O bond related intrinsic defects.