AbstractControlling the nanomorphology in bulk heterojunction photoactive blends is crucial for optimizing the performance and stability of organic photovoltaic (OPV) technologies. A promising approach is to alter the drying dynamics and consequently, the nanostructure of the blend film using solvent additives such as 1,8‐diiodooctane (DIO). Although this approach is demonstrated extensively for OPV systems incorporating fullerene‐based acceptors, it is unclear how solvent additive processing influences the morphology and stability of nonfullerene acceptor (NFA) systems. Here, small angle neutron scattering (SANS) is used to probe the nanomorphology of two model OPV systems processed with DIO: a fullerene‐based system (PBDB‐T:PC₇₁BM) and an NFA‐based system (PBDB‐T:ITIC). To overcome the low intrinsic neutron scattering length density contrast in polymer:NFA blend films, the synthesis of a deuterated NFA analog (ITIC‐d₅₂) is reported. Using SANS, new insights into the nanoscale evolution of fullerene and NFA‐based systems are provided by characterizing films immediately after fabrication, after thermal annealing, and after aging for 1 year. It is found that DIO processing influences fullerene and NFA‐based systems differently with NFA‐based systems characterized by more phase‐separated domains. After long‐term aging, SANS reveals both systems demonstrate some level of thermodynamic induced domain coarsening.