This study presents a first detailed investigation of the energetics and dynamics of dissociation of peptide radical cations using a model system, in which the initial position of the radical site is well-defined. We demonstrate that fragmentation is dominated by bond cleavages that are remote from the initial position of the radical site and that all the dissociation channels are adequately described by the RRKM theory. Our findings suggest that fragmentation of peptide radical cations does not circumvent the ergodic assumption.