We study the photodissociation induced by ultraviolet excitation of amide bonds in gas-phase protonated peptides. Jointly, mass spectrometry and cold ion spectroscopy provide evidence for a selective non-statistical dissociation of specific peptide bonds in the spectral region of the formally forbidden n→π* transition of amide groups. Structural analysis reveals that the activation of this transition, peaked at 226 nm, originates from the non-planar geometry of the bond. In contrast, the statistical dissociation in the electronic ground state appears to be the main outcome of the π→π* excitation of the peptide bonds at 193 nm. We propose a tentative model that explains the difference in the fragmentation mechanisms by the difference in localization of the electronic transitions and the higher amount of vibrational energy released in the electronic excited state upon absorption at 193 nm.