The effect of nanoscopic cylindrical confinement on the crystal structures and crystallization behaviors of Bi was investigated. While the crystallites of Bi nanorods were found to have a higher orientation proportional to the degree of confinement, an alteration of the crystal orientation between electrodeposited and recrystallized Bi nanorods was observed. Thermal analysis confirmed a structural difference between the as-deposited and recrystallized nanorods and that a crystallization mechanism where nucleation determines the overall rate of crystallization occurred during recrystallization. The crystal structure, including the preferred crystal orientation, is discussed in terms of the dominant crystallization mechanism under the cylindrical nanoconfinement. (c) 2007 Elsevier B.V. All rights reserved.