Reduction of Ge(OBu)4 with PhMe2SiH catalyzed by B(C6F5)3 at ambient temperature leads to GeH4. We discovered that a higher temperature (above 100 °C) completely changes the reaction course by producing germanium nanoparticles (Ge NPs) in high yield. This process provides a simple one-pot method for Ge NPs synthesis from readily available substrates under mild conditions.