The aim of this Thesis is to rationalize, from a theoretical perspective, the structural, electronic, optical and transport properties of different electroactive non-covalent assemblies of special relevance in the field of organic electronics. The ultimate goal is to establish valuable supramolecular structure-property relationships. In particular, this Thesis is focused on three types of systems: hole transporting materials (HTM), donor–acceptor supramolecular complexes and supramolecular polymers. For each system, the spotlight has been put on different relevant electronic processes. In the first part, the structural organization of several supramolecular polymers is studied. In particular, the relation between the supramolecular organization and the properties of interest (e.g. chiral behavior, or optical properties) of the selected systems. In the second part the charge transport properties of hole transporting materials, donor–acceptor supramolecular complexes are studied. On one hand the effect of H-bonding and the size of the HTM in the electronic mobilities is investigated. On the other hand, the kinectics of the photoinduced electron transfer on donor–acceptor supramolecular complexes in solution is simulated. Finally, the effects that become relevant for energy transport at the typical distances found in non-covalent assemblies are analyzed. These findings are used to simulate the exciton dynamics along one supramolecular polymer and, in particular the role of the charge transfer states in the exciton transport is analyzed.