We report that nanometric bismuth can directly be electrodeposited at room temperature without the use of a nanoporous template. The morphology, microstructure, and purity of the as-prepared electrodeposits were characterized by scanning electron microscopy, transmission electron microscopy, and infrared spectroscopy. Typically, well-crystallized nanometer-sized particles of Bi ranging from 10 to 20 nm are obtained. The key to success of such a process lies in the electrochemical coreduction of pyrocatechol violet during the bismuth deposition, which disturbs the electrocrystallization process. As a first possible application, we show that Bi/Cu nanoarchitectured electrodes exhibit interesting rate capabilities when used as electrode material vs Li. (c) 2007 The Electrochemical Society.