The thermoelectric material Bi80Sb20 was grown by high temperature melt-quench growth method and characterized by powder XRD. The Rietveld refinements revealed the presence of Bi80Sb20 and also the elemental parents Bi and Sb. All the three phases were analyzed and the electron density distribution and local structure of Bi, Sb and Bi80Sb20 were individually studied. The bonding between the atoms was studied using maximum entropy method (MEM). A comparison of 3D and 2D electron density distributions of Bi, Sb and Bi80Sb20 on the (110) and (024) planes clearly shows highly concentrated and localized electron clouds in Bi80Sb20 supporting the use of BiSb alloy as a thermoelectric material. (C) 2009 Elsevier B.V. All rights reserved.