The fabrication, by an all electrochemical process, of porous Si/ZnO nanostructures with engineered structural defects, leading to strong and broadband deep level emission from ZnO, is presented. Such nanostructures are fabricated by a combination of metal-assisted chemical etching of Si and direct current electrodeposition of ZnO. It makes the whole fabrication process low-cost, compatible with Complementary Metal-Oxide Semiconductor technology, scalable and easily industrialised. The photoluminescence spectra of the porous Si/ZnO nanostructures reveal a correlation between the lineshape, as well as the strength of the emission, with the morphology of the underlying porous Si, that control the induced defects in the ZnO. Appropriate fabrication conditions of the porous Si lead to exceptionally bright Gaussian-type emission that covers almost the entire visible spectrum, indicating that porous Si/ZnO nanostructures could be a cornerstone material towards white-light-emitting devices.