Two hydride catalysts [Fe(CO)(dppp)H(NO)] (dppp = 1,3-bis(diphenylphosphino)propane) and [Fe(CO)H(NO)(PPh3)2] in comparison with nonhydride analogues [Fe(dppe)(NO)2] (dppe = 1,3-bis(diphenylphosphino)ethane) and [Fe(NO)2(PPh3)2] are investigated with a combination of valence-to-core X-ray emission spectroscopy (VtC-XES) and high-energy resolution fluorescence detected X-ray absorption near-edge structure (HERFD-XANES). To fully understand the experiments and to obtain precise information about molecular levels being involved in the spectral signals, time-dependent density functional theory (TD-DFT) calculations and ground state density functional theory (DFT) calculations are necessary. An excellent agreement between experiment and theory allows the identification of particular spectral signals of the Fe-H group. Antibonding Fe-H interactions clearly contribute to pre-edge signals in HERFD-XANES spectra, while bonding Fe-H interactions cause characteristic signatures in the VtC-XES spectra. The sensitivity of both methods with respect to the Fe-H distance is demonstrated by a scanning simulation approach. The results open the way to study metal hydride complexes in situ, their formation, and their fate during catalytic reactions, using high-resolution XANES and valence-to-core X-ray emission spectroscopy.