Neutral peptides of natural amino acids of the type (X)(n)-Y (n = 1,2,3) are prepared in the gas phase by laser desorption and supersonic cooling. Local ionization is performed by resonant laser excitation in aromatic amino acids (Y) located at the C-terminal end. In a one-color experiment, subsequent UV photofragmentation of the cation is shown to directly reflect the prior charge migration in these large molecules. Peptides are engineered, which show either fragment ions originating from the chromophore or from the opposite N-terminal side (X). The results show that by changing local ionization energies and thus absolute positions of ionic dissociation energies, one has complete control over different paths of chemical reactivity. The length dependence of the process shows, that charge mobility seems to be not the bottleneck for dissociation pathways at high internal energies : charge transfer over more than 10 sigma-bonds is shown. When we apply a local picture and estimate local ionization potentials, we find, for the peptides used here, that after localized ionization, positive charge is statically localized at the initial prepared site. In a two-color experiment (UV + VIS) we observe indications that in the photoexcited tripeptide cation Leu-Leu-Tyr charge transfer can occur at internal energies of about 2.2 eV, an energy at which no dissociation occurs. We interpret the process in terms of direct photoexcitation into a charge transfer (CT) band or by a photoexcitation to a localized state followed by nonradiative relaxation to a CT state. For the charge-transfer process we propose a through bond HOMO electron transfer (hole transfer) as the relevant mechanim. Consequences of our findings for charge migration and fragmentation processes in peptides are discussed.