K beta X-ray emission spectroscopy (XES) is emerging as a powerful tool for the study of chemical bonding. Analyses of the K beta XES of ferrocene (Fc) and ferrocenium (Fc(+)) are presented as further demonstrations of the capabilities of the technique. Assignments of the valence to core (V2C) region of these spectra as electric dipole-allowed cyclopentadienyl (Cp) -> Fe Is transitions demonstrate that XES affords electronic structural insight into the energetics of ligand-based molecular orbitals (MOs). Combined with K-edge X-ray absorption spectroscopy (XAS), we show that XES can provide analogous information to photoemission spectroscopy (PES). Density functional theory (DFT) analyses reveal that the V2C transitions in Fc/Fc(+) derive their intensity from Fe 4p admixture (on the order of 5-10%) into the Cp-based MOs from which they originate. These 4p admixtures confer bonding character to the Cp-based a(2u) and e(1u), MOs to at least the extent of backbonding contributions to frontier MOs from higher-lying Cp pi* MOs.