For the first time, we synthesized a carbon nanotubes–GeO₂ nanocomposite via a facile one-pot solution method. The as-prepared carbon nanotubes–GeO₂ nanocomposite appears as webs of curved nanotubes and nanoparticles, forming strong intertwined entanglements with a three-dimensional (3D) network structure. Such a hybrid structure can not only greatly improve the electron conductivity of the nanocomposite, but also effectively buffer the volume change of GeO₂ during the charge–discharge process. The carbon nanotubes–GeO₂ nanocomposite retains 813.7 mA h g⁻¹ even after 500 cycles at the current rate of 0.2 A g⁻¹ as an electrode material for Li ion batteries (LIBs) and shows high rate capability at variable current rates.