High energy resolution fluorescence detected XANES (HERFD-XANES) and valence-to-core X-ray emission spectroscopy (VtC-XES) are introduced as powerful tools to investigate hydride-iron interaction, the possible iron-iron bond, and iron spin state of the dinuclear tetra-hydrido complex [{(CpFe)-Cp-5}(2)(mu-H)(4)] (1H, Cp-5 = eta(5)-C(5)iPr(5)) by thoroughly accessing the geometric and electronic structure of this complex in comparison to the nonhydride reference [(CpCpFe)-Cp-5] (1, Cp = C5H5). The so far observed most intense hydride induced signals in the pre-edge feature of the HERFD-XANES and in the VtC-XES spectra at the iron Kedge allow a precise analysis of the LUMO and HOMO states, respectively, by application of time-dependent density function theory (TD-DFT) and density functional theory (DFT) calculations. The results of these calculations are further employed to understand the oxidation state, spin states, and potential Fe-Fe bonds in this complex.