The weak pre-edge features in the Mn K-edge X-ray absorption near-edge structure (XANES) spectrumof manganese monoxide (MnO) were investigated by comparing experimental data with dipolar and quadrupolarcross-section calculations in the framework of multiple-scattering theory. We assign the first pre-edge feature to a di-rect quadrupolar transition from Is core state to 3d molecular orbitals of the central atom, e.g., the lowest in energy,due to the more effective attraction of the core hole. The second peak in this region arises unambiguously from thehybridization between p-orbitals of the central atom with higher-shell metal octahedral orbitals.