The vibrational coupling in the ground and excited states of positively charged naphthalene, anthracene, tetracene, and pentacene molecules is studied on the basis of a joint experimental and theoretical study of ionization spectra using high-resolution gas-phase photoelectron spectroscopy and first-principles correlated quantum-mechanical calculations. Our theoretical and experimental results reveal that, while the main contribution to relaxation energy in the ground state of oligoacene systems comes from high-energy vibrations, the excited-state relaxation energies show a significant redistribution toward lower-frequency vibrations. A direct correlation is found between the nature of the vibronic interaction and the pattern of the electronic state structure.