The unconventional superconductivity in the newly discovered iron-based superconductors is intimately related to its multi-band/multi-orbital nature. Here we report the comprehensive orbital characters of the low-energy three-dimensional electronic structure in BaFe1.85Co0.15As2 by studying the polarization and photon energy dependence of angle-resolved photoemission data. While the distributions of the dxz, dyz, and d 3z 2 −r 2 orbitals agree with the prediction of density functional theory, those of the dxy and d x 2 −y 2 orbitals show remarkable disagreement with theory. Our results point out the inadequacy of the existing band structure calculations, and more importantly, provide a foundation for constructing the correct microscopic model of iron pnictides.