The molecular parameters governing charge transport along a pi-stacked fluorene chain in poly(dibenzofulvene) are studied by a joint experimental and theoretical approach involving high-resolution gas-phase photoelectron spectroscopy and quantum-mechanical methods. We specifically investigate the electronic couplings between fluorene moieties as well as the intramolecular reorganization energies, for both holes and electrons. Our results indicate that a pi-stacked fluorene chain favors hole transport over electron transport. The values for electronic couplings and reorganization energies estimated here are compared with those derived recently for pentacene.