Spectrally dependent steady-state photoconductivity is a convenient method to gain insight into the charge generation and transport processes within a given material. In this work, we report on the photoconductive response of solution-processed neat films and blends of the fullerene, PC(71)BM, and the donor-acceptor small-molecule, p-DTS(PTTh(2))(2), as function of the processing additive, diiodooctance (DIO). The results, when considered in the context of their structural, optical, and electronic properties give insight into the dominant carrier generation and charge transport mechanisms in each of these molecular systems.