We present spatially resolved vibronic spectroscopy of individual pentacene molecules in a double-barrier tunneling junction. It is observed that even for this effective single-level system the energy dissipation associated with electron attachment varies spatially by more than a factor of 2. This is in contrast to the usual treatment of electron-vibron coupling in the Franck-Condon picture. Our experiments unambiguously prove that the local symmetry of initial and final wave function determines the dissipation in electron transport. © 2013 American Physical Society.