High-capacity anode materials based on alloy-type group IV elements always have large volume expansion during lithiation when they are used in lithium-ion batteries. Designing hollow structures is a well-established strategy to accommodate the volume change because of sufficient internal void space. Here we report a facile template-free route to prepare hollow Ge nanospheres without using any templates through a quasi-microemulsion method. Ge nanocrystals are preferably self-assembled along the interface of liquid vesicles between water and tetrahydrofuran, and well-defined hollow architectures of ∼50 nm in diameter are formed. Both the wall thickness and hollow interiors can be easily tuned. After subsequent carbon coating via pyrolysis of acetylene, the as-formed Ge@C nanocomposite with hollow interiors exhibits a highly reversible capacity of about 920 mA h g(-1) at 200 mA g(-1) over 50 cycles, and excellent rate capability. The small size and the high structural integrity of hollow Ge@C structures contribute to the superior lithium-storage performances.