The formation mechanism of a spray-coated film is different from that of a spin-coated film. This study employs grazing incidence small- and wide-angle X-ray Scattering (GISAXS and GIWAXS, respectively) quantitatively and systematically to investigate the hierarchical structure and phase-separated behavior of a spray-deposited blend film. The formation of PCBM clusters involves mutual interactions with both the P3HT crystal domains and droplet boundary. The processing control and the formed hierarchical structure of the active layer in the spray-coated polymer/fullerene blend film are compared to those in the spin-coated film. How the different post-treatments, such as thermal and solvent vapor annealing, tailor the hierarchical structure of the spray-coated films is quantitatively studied. Finally, the relationship between the processing control and tailored BHJ structures and the performance of polymer solar cell devices is established here, taking into account the evolution of the device area from 1 × 0.3 and 1 × 1 cm(2). The formation and control of the special networks formed by the PCBM cluster and P3HT crystallites, respectively, are related to the droplet boundary. These structures are favorable for the transverse transport of electrons and holes.