Germanium-based materials possess promising potential as novel anode materials for high performance lithium-ion batteries (LIBs). However, the considerably huge volume change causes rapid capacity fade during the charge-discharge process. A simple strategy was devised to prepare porous GeO2 nanoparticles via thermal decomposition of (Hbipy)2[Ge(C2O4)3]·2H2O in air atmosphere. As an anode material for LIBs, it shows superior electrochemical performance in comparison with commercial GeO2 microparticles. The initial discharge capacity of porous GeO2 nanoparticles is high to 2578.8mAh/g, and it still retained 581.9mAh/g after 100 cycles. Even at 2A/g, a reversible discharge capacity of 184.2mAh/g is yet obtained. The superior lithium storage performances should be chalked up to the positive synergism of nanoscale, porous structure and low crystalline nature, which effectively retard the huge volume change of GeO2 and are beneficial for fast diffusion of lithium ions during cycling.