We experimentally demonstrate polarization-selective two-dimensional (2D) vibrational-electronic (VE) spectroscopy on a transition-metal mixed-valence complex where the cyanide stretching vibrations are coupled to the metal-to-metal charge-transfer transition. A simultaneous fitting of the parallel and crossed polarized 2D VE spectra quantifies the relative vibronic coupling strengths and angles between the charge-transfer transition and three coupled cyanide stretching vibrations in a mode-specific manner. In particular, we find that the bridging vibration, which modulates the distance between the transition-metal centers, is oriented nearly parallel to the charge-transfer axis and is 9 times more strongly coupled to the electronic transition than the radial vibration, which is oriented almost perpendicular to the charge-transfer axis. The results from this experiment allow us to map the spectroscopically observed vibronic coordinates onto the molecular frame providing a general method to spatially resolve vibronic energy transfer on a femtosecond time scale.