Organic photovoltaics (OPV) are close to reaching a landmark 20% device efficiency. One of the proposed reasons that OPVs have yet to attain this milestone is their propensity toward triplet formation. Herein, a small molecule donor, DRCN5T, is studied using a variety of morphology and spectroscopy techniques, and blended with both fullerene and non-fullerene acceptors. Specifically, grazing incidence wide-angle X-ray scattering and transient absorption, Raman, and electron paramagnetic resonance spectroscopies are focused on. It is shown that despite DRCN5T's ability to achieve OPV efficiencies of over 10%, it generates an unusually high population of triplets. These triplets are primarily formed in amorphous regions via back recombination from a charge transfer state, and also undergo triplet-charge annihilation. As such, triplets have a dual role in DRCN5T device efficiency suppression: they both hinder free charge carrier formation and annihilate those free charges that do form. Using microsecond transient absorption spectroscopy under oxygen conditions, this triplet-charge annihilation (TCA) is directly observed as a general phenomenon in a variety of DRCN5T: fullerene and non-fullerene blends. Since TCA is usually inferred rather than directly observed, it is demonstrated that this technique is a reliable method to establish the presence of TCA
