We have deposited the c-axis-oriented orthorhombic TbMnO3 (o-TMO) films with well-aligned in-plane orientations on NdGaO3 (001) substrates by using pulsed laser deposition. The distinctive orientation alignments between the film and substrate allow the study of the X-ray absorption spectroscopy (XAS) with the electric field along three major crystallographic directions, respectively. Polarization-dependent XAS spectra show significant anisotropy in the electronic Structure of o-TMO. The correlation between the electronic structure, the bonding anisotropy, and the magnetoelectric effect in the multiferroic materials is revealed. (C) 2009 Elsevier B.V. All rights reserved.