GeO2 is a promising anode material for lithium ion batteries due to its high theoretical capacity (1126 mAh g−1 for reversibly storing 4.4 Li+), and moderately low operating voltage (<1.5 V). Nevertheless, the fabrication of truly durable GeO2 anode with satisfactory rate capability and cycling stability remains a big challenge because of its inherent low conductivity, and the large volume expansion upon charge-discharge that causes severe capacity fading. In this study, an innovative nanostructure with size-adjustable GeO2 nanoparticles (16–26 nm) embedded in continuous S-doped carbon (GeO2/S-doped carbon, GSC) has been successfully fabricated via a facile in-situ simultaneous polymerization method followed by heat treatment. The electrochemical results indicate that the as-prepared GSC composites show high reversible capacity (672.9 mAh g−1 at 50 mA g−1), superior rate capability (332.9 mAh g−1 at 1000 mA g−1), and long-term cycle life (179 mAh g−1 after 500 cycles at 1000 mA g−1) as anode materials for lithium ion batteries.