The helical nanofilament (HNF) liquid crystal phase is an ordered architecture exhibiting interesting properties for charge transport. It is a small molecule self-assembly of stacked and twisted crystalline layers, which form alignable organic nanorods with half the surface area of the filaments consisting of aromatic sublayer edges. HNFs mixed with an electron acceptor generate an intriguing network for photoinduced electron transfer (PET). In this work, we characterize the structure of the HNF phase as processed into thin films with transmission electron microscopy (TEM) and X-ray diffraction (XRD). Additionally, we measure the flash-photolysis time-resolved microwave conductivity (TRMC) in samples where the HNF phase is fabricated into heterojunctions with the fullerenes C60 and PC60BM, prototypical electron acceptors for organic photovoltaics. Two distinct microstructures of the thin films were identified and compared for PET. A near-unity charge generation yield is observed in a bilayer of HNFs with C60. Moreover, the HNF phase is shown to be 10× better at charge generation than a lamellar structuring of the same components. Thus, the HNF phase is shown to be a good charge-generation interface.