Herein, novel single-crystalline Ge nanotetrahedrons with dominantly exposed (102) facets are synthesized via a liquid-phase chemical reduction strategy. Polyvinyl pyrrolidone is innovatively employed to mediate the product morphology, while the reaction time also plays a significant role. As the anode materials for lithium ion batteries, the nanoscale size effect, highly active crystal planes and lightened agglomeration guarantee the excellent performance of Ge nanotetrahedrons. They could maintain a capacity of 730 mAhg^–1 after 100 cycles at 160 mAg^–1, and exhibited greatly enhanced rate capability when compared with Ge random nanoparticles.