Layers of germanium (Ge) microrods with a core–shell structure on titanium foils were grown by a metal-assisted electrochemical reduction of germanium oxide in aqueous electrolytes. The structural properties and composition of the germanium microrods were studied by means of scanning and transmission electron microscopy. Electrochemical studies of germanium nanowires were carried out by impedance spectroscopy and cyclic voltammetry. The results showed that the addition of vinylene carbonate (VC) in the electrolyte significantly reduced the irreversible capacity during the first charge/discharge cycles and increased the long-term cycling stability of the Ge microrods. The obtained results will benefit the further design of Ge microrods-based anodes that are formed by simple electrochemical deposition.