The near threshold photofragmentation pattern of δ- valerolactam+ and δ-valerolactam2+ has been recorded combining electron/ion coincidence techniques and vacuum ultraviolet synchrotron radiation. The experimental method yields the fragment intensity as a function of the internal energy deposited into the parent cation, up to 3.1 eV above the first ionization threshold. In parallel, ab initio studies on the δ-valerolactam+ and δ-valerolactam2 + cations and their ionic and neutral fragmentation products have been performed with the aim of determining the isomers of the ionic products observed experimentally as well as of their neutral counterparts. These computations were performed using the PBE0 exchange-correlation functional and the augcc- pVDZ basis set. We found good agreement between the calculated reaction enthalpies and experimental appearance energies of the ions. More generally, our experimental and theoretical results reveal that the fragmentation of the ionic species of interest leads to a multitude of neutral and ionic fragments, which may be formed after intramolecular isomerization and complex decomposition processes. Multistep reaction pathways are expected.