understood. Triplet behavior in organic solar cells is one of the most understudied aspects. The reason of the relatively low number of studies is that triplet formation is typically considered a loss pathway, and thus associated with systems with low device efficiencies. Indeed, many previous studies indicated that triplets were formed only when charge separation did not occur or was very inefficient. [3][4][5][6] As such, triplets were considered irrelevant for the highest efficiency OPV devices. However, it has recently been demonstrated that OPV blends with non-fullerene acceptors (NFAs), the main driver of the current record OPV efficiencies, can show pronounced triplet formation and yet still provide high efficiencies. [7] In the benchmark PM6:Y6 blend, for example, NFA triplet exciton formation accounts for 90% of charge recombination at open circuit, leading to a 60 mV reduction of the open circuit voltage. As such, it is important to elucidate triplet pathways in organic solar cells, in particular how they affect charge photogeneration and recombination. Triplets can be generated via several different pathways in organic solar cells. [8,9] First, the photogenerated singlet exciton can undergo intersystem crossing (ISC). Second, triplets can form via charge transfer (CT) states at the donor/acceptor interface. These CT states can undergo rapid spin-mixing due to the low exchange energy between 3 CT and 1 CT states, often 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.