<jats:title>Abstract</jats:title>
<jats:p>Charge transfer (CT) state is a key intermediate to understand recombination processes in organic solar cells (OSCs). In this study, we measured the recombination emission from the CT state under different applied voltages in OSCs and a photocurrent density flowing on the circuit simultaneously. We proposed a “photoluminescence (PL)<jats:italic>–</jats:italic>voltage (<jats:italic>V</jats:italic>) plot” that is the voltage dependence of PL intensity of the CT state. The PL<jats:italic>–V</jats:italic> plot includes information only from the CT state recombination at the donor/acceptor interface and is complementary to the “current density (<jats:italic>J</jats:italic>)<jats:italic>–V</jats:italic> plot” that is the most important information for evaluating OSCs. The results demonstrated that the fill factor (FF) of the PL<jats:italic>–V</jats:italic> plot is higher than that of the <jats:italic>J–V</jats:italic> plot, predicting the ideal FF of the device. Our result demonstrated that the simultaneous measurement of photocurrent and recombination emission could be a strong tool for evaluating photoconversion characteristics in OSCs.</jats:p>
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