While the geometric and electronic structures of vitamin B-12 (cyanocobalamin, CNCbl) and its reduced derivatives Co(2+)cobalamin (Co(2+)Cbl) and Co(1+)cobalamin (Co(1+)Cbl(-)) are now reasonably well established, their vibrational properties, in particular their resonance Raman (rR) spectra, have remained quite poorly understood. The goal of this study was to establish definitive assignments of the corrin-based vibrational modes that dominate the rR spectra of vitamin B-12 in its Co3+, Co2+, and Co1+ oxidation states. rR spectra were collected for all three species with laser excitation in resonance with the most intense corrin-based pi -> pi* transitions. These experimental data were used to validate the computed vibrational frequencies, eigenvector compositions, and relative rR intensities of the normal modes of interest as obtained by density functional theory (DFT) calculations. Importantly, the computational methodology employed in this study successfully reproduces the experimental observation that the frequencies and rR excitation profiles of the corrin-based vibrational modes vary significantly as a function of the cobalt oxidation state. Our DFT results suggest that this variation reflects large differences in the degree of mixing between the occupied Co 3d orbitals and empty corrin pi* orbitals in CNCbl, Co(2+)Cbl, and Co(1+)Cbl(-). As a result, vibrations mainly involving stretching of conjugated C-C and C-N bonds oriented along one axis of the corrin ring may, in fact, couple to a perpendicularly polarized electronic transition. This unusual coupling between electronic transitions and vibrational motions of corrinoids greatly complicates an assignment of the corrin-based normal modes of vibrations on the basis of their rR excitation profiles.