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We present two-dimensional white-light spectroscopy (2DWL) measurements of binary and ternary bulk heterojunctions of the polymer donor PM6 mixed with state-of-the-art nonfullerene acceptors Y6 or IT4F. The ternary film has a shorter lifetime and faster spectral diffusion than either of the binary films. 2D line shape analysis of the PM6 ground state bleach with a Kubo model determines that all three films have similar amplitudes of fluctuations (Δ = 0.29 fs–1) in their transition frequencies, but different relaxation times (ranging from 102 to 24 fs). The ternary film exhibits faster dynamics than either of the binary films. The short lifetime of the ternary blend is consistent with increased photoexcitation transfer and the fast frequency fluctuations are consistent with structural dynamics of aliphatic side chains. These results suggest that the femtosecond fluctuations of PM6 are impacted by the choice of the acceptor molecules. We hypothesize that those dynamics are either indicative, or perhaps the initial source, of structural dynamics that ultimately contribute to solar cell operation.