Charge transfer and fragmentation in collisions of sodium cluster ions with caesium atoms have been investigated theoretically within a microscopic framework called Non-adiabatic Quantum Molecular Dynamics. To illustrate the complexity of non-adiabatic cluster collisions, in particular the interplay between charge transfer and fragmentation, Na + 4 (2.7 keV) + Cs collisions are studied in detail with special emphasis on methodical aspects. It is shown that integral and exclusive charge transfer cross sections can be understood only if all types of fragmentation processes including statistical decay are taken into account. The influence of the cluster structure (isomers, temperature, size) on measured and measurable cross sections is studied for different charge transfer channels as well as for fragmentation. In particular, cross sections for the exotic formation of caesium anions in such collisions are predicted.