Bi(2)O(3) is an important metal oxide in catalysis. In this paper we employed density functional theory and slab model to investigate the surface energies and structures of various α-Bi(2)O(3) surfaces. We first studied ten different terminations along [100] direction which has both polar and nonpolar terminations due to alternating stacking of Bi layers and O layers. Our calculated surface free energies show that the stoichiometric symmetric terminations are most stable at both high and low oxygen pressures, followed by the T(2O)/T(4O) terminations at low/high oxygen pressures. In the low Miller index planes, the (010) plane is the most stable whereas the (110) plane is the least stable. Analyses reveal that relaxation may change the surface structures significantly and there is a nice linear relationship between the surface density of broken short Bi-O bonds and the surface energy before relaxation.