Diamond electrodes are attractive for chemical and biological sensing but require high substrate temperatures (T > 700 degrees C) for chemical vapor deposition and are therefore limited to temperature-tolerant substrates. Boron-doped, polycrystalline diamond electrode arrays on temperature-sensitive polymer substrates were fabricated using a "diamond-first" transfer process. This transfer process rendered the normally inaccessible smooth nucleation surface of the diamond film as the active electrode surface. Cyclic voltammetry demonstrated the basic electrochemical functionality of the transferred diamond electrode by detection of 100 mu M dopamine, and Raman spectroscopy measurements showed the electrode surface structure to be similar to that of the typical diamond growth surface. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3479691] All rights reserved.