Solution deposition using high-boiling-point additives such as octanedithiol (ODT) provides a simple and widely used fabrication option for improving the power conversion efficiencies of solar cells composed of narrow-band-gap conjugated polymer donor/fullerene acceptor blends. Previous examination of the resulting device active layers has shown that the use of additives influences the degree of phase segregation within the bulk heterojunction (BHJ) blend and also improves ordering within the polymeric domains. In this work, in situ grazing-incidence wide-angle X-ray scattering as a function of time was used to explore the dynamics of the BHJ evolution. These studies showed that a small percentage of ODT in chlorobenzene (CB) induced the nucleation of polymeric crystallites within 2 min of deposition, increased the orientational order of specific polymorphs, and promoted further crystallite nucleation over a period longer than 40 min after casting. Similar structural changes did not occur when the same BHJ blend was cast from pure CB.