Films of the semiconducting polymer poly4,8-bis(2-ethylhexyl)oxybenzo1,2-b:4,5-b′dithiophene-2,6-diyl3-fluoro-2-(2-ethylhexyl)carbonylthieno3,4-bthiophenediyl with 40% fluorinated monomers, denoted PTB7-F40, are spin coated out of different solvents onto PEDOT:PSS films. The influence of the used solvents chlorobenzene, 1,2-dichlorobenzene, and 1,2,4-trichlorobenzene as well as the influence of the additive 1,8-diiodooctane (DIO) is probed with grazing incidence small- and wide-angle X-ray scattering (GISAXS and GIWAXS). As seen with GISAXS, without DIO, the films are homogeneous and show roughness correlation with the PEDOT:PSS film surface. With DIO, an inner film structure with a size of 50–75 nm is found and the roughness correlations weaken. In addition, as seen in GIWAXS, the crystalline part of the films is influenced by the used solvent if DIO is added.