Improving device performance and extending Moore's Law can be aided through active solid-state cooling, using thermoelectric (TE) materials with a high figure of merit (zT > 1). TE nanowires promise a path to higher zT, and electrochemical deposition (ECD) is a simple and scalable means for synthesizing TE nanowires. In this paper we report the ECD of 75 nm diameter nanowire arrays with a nominal composition of Bi-2(Te0.95Se0.05)(3) onto Si substrates. These nanowires show an improved level of compositional control than previously observed for TE nanowires in this system by ECD. This results from our new non-aqueous bath combined with recently described methods for template formation on Si. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.084204jes] All rights reserved.