Novel trinuclear rhodium-hydride complexes with diphosphine ligands Tangphos, t-Bu-BisP*, and Me-DuPHOS which contain bridging mu(2)- and mu(3)-hydrides as well as terminal hydrides in one molecule have been reported recently. In this work, these different rhodium-hydride bonds are characterized by Raman spectroscopy and the results are compared with those obtained by means of the more commonly applied IR spectroscopy. Density functional theory (DFT) calculations have been carried out to support the experimental findings. The structure of the Rh3H7 core is described in the context of their vibrational stretching modes.