Ultrafast charge delocalization dynamics in an internal donor–acceptor copolymer poly(9,9-dioctylfluorenyl-co-bithiophene) (F8T2) and its blend with the fullerene derivative [6,6]-phenyl C₆₁ butyric acid methyl ester (PCBM) was studied by resonant Auger spectroscopy measured around sulfur K-edge using the core-hole clock approach. The effect of thermal annealing on the charge transfer delocalization times (τ_CT) was also investigated. Two main transitions with S 1s → π* and S 1s → σ*(S–C) character were measured at the S 1s NEXAFS spectra. Poor charge delocalization was observed for as cast polymeric films at photon energies corresponding to the S 1s → π* transition, which may suggest a weak π-electronic coupling due to weak polymer crystallinity and chain stacking. Enhancement in the charge transfer process for photon energies close to the resonance maximum was observed for thermally annealed F8T2 and its blends. Atomic Force Microscopy (AFM) topography for as cast F8T2:PCBM shows a top position of PCBM units relative to the polymer, homogeneously distributed on the film surface. This configuration improves the charge delocalization through S 1s → π* molecular orbitals for the as cast blended film, suggesting a strong π-electronic coupling. A new rearrangement of F8T2:PCBM film was found after thermal annealing, leading to a more efficient electron transfer channel through σ* molecular orbitals.