A diketopyrrolopyrrole (DPP) and perylene diimide (PDI)-based molecule, denoted as PDI-DPP-PDI, was investigated as an electron acceptor material in bulk heterojunction (BHJ) solar cells, with poly[[4,8-bis [5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl] [2-(2-ethyl-1-oxohexyl)thieno[3,4-b]thiophenediyl]] (PBDTTT-CT) as an electron donor. The donor polymer and the acceptor molecule have complementary absorption spectra, which is an essential feature for energy collection in organic solar cells. However, AFM images indicated the presence of isolated and microsized PDI-DPP-PDI domains along the surface of the films, which reduced the power conversion efficiency. Therefore, to improve the homogenization of the acceptor along the film, a post-deposition treatment, denoted as solvent vapor annealing (SVA), was performed in a saturated atmosphere containing the vapour of an organic solvent for 3-10 minutes. This procedure changed the optical and morphological properties of the PBDTTT-CT : PDI-DPP-PDI active layer, resulting in increased power conversion efficiency values by more than 2.5 times (reaching 5.1%). Theoretical simulation pointed out that the experimental absorbance band localized at 580 nm, which appeared after SVA treatment, is possibly related to an intense simulated band with a maximum at 572 nm, resulting from a pair of transitions starting in the copolymer and ending in PDI-DPP-PDI, in regions where both are stacked at about 3 Å. The most significant natural transition orbitals (NTOs) related to these transitions indicated charge transfer character. Moreover, analyses carried out by power spectrum density (PDS) of images acquired from the SVA-treated film indicated that in the region of larger frequencies, across the length scale at around 30-70 nm, an additional fractal region appeared with a Ds of 0.95, indicating a flattened region, possibly related to changes in the overall conformation after SVA treatment. This indicates an improvement in the molecular packing, a feature not observed in the as-cast film. The analyses by force curve spectroscopy pointed out increased adhesion forces and adhesion energy in the PBDTTT-CT : PDI-DPP-PDI film after SVA treatment; this feature enhanced the interfacial interaction with the top electrodes, reflecting improved charge extraction in the photovoltaic device.