The addition of polystyrene (PS), a typical insulator, is empirically shown to increase the power conversion efficiencies (PCEs) of a solution-deposited bulk heterojunction (BHJ) molecular blend film used in solar cell fabrication: p-DTS(FBTTh2)2/PC71BM. The performance is further improved by small quantities of diiodooctane (DIO), an established solvent additive. In this study, how the addition of PS and DIO affects the film formation of this bulk heterojunction blend film are probed via in situ monitoring of absorbance, thickness, and crystallinity. PS and DIO additives are shown to promote donor crystallite formation on different time scales and through different mechanisms. PS-containing films retain chlorobenzene solvent, extending evaporation time and promoting phase separation earlier in the casting process. This extended time is insufficient to attain the morphology for optimal PCE results before the film sets. Here is where the presence of DIO comes into play: its low vapor pressure further extends the time scale of film evolution and allows for crystalline rearrangement of the donor phase long after casting, ultimately leading to the best BHJ organization. In situ measurement shows that polystyrene (PS) and diiodooctane (DIO) additives promote donor crystallite formation synergistically, on different time scales, and through different mechanisms. PS-rich films retain solvent, promoting phase separation early in the casting process. Meanwhile, the low vapor pressure of DIO extends the time scale of film evolution and allows for crystalline rearrangement of the donor phase after casting. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.