A non-fullerene small molecular acceptor (NFA) is a prominent molecule that shows moderate electron mobility and a narrow bandgap complementary to middle-bandgap p-type conjugated polymers, which leads to great improvement in the performance of organic photovoltaic (OPV) cells. However, little is known about the relaxation of charge carriers, which is key to efficient charge transport. Herein, we report simultaneous time-of-flight (TOF) and time-resolved microwave conductivity (TRMC) measurements[1] employing benzodithiophene-based polymer (PBDB-T):soluble C70-fullerere (PCBM) and PBDB-T:NFA (ITIC or Y6) blends, as benchmark systems[2, 3]. In addition to the conventional TOF mobilities, relaxation of the hole and electron mobility was evaluated by TRMC under an external electric field. Although PBDB-T:ITIC exhibited much faster relaxation than PBDB-T:PCBM, the relaxation in PBDB-T:Y6 was considerably moderate. This is consistent with the energetic disorder estimated from the photoabsorption onset. Interestingly, the slower relaxation of the electrons compared to the holes in PBDB-T:Y6 is in line with the preferred normal device structure. Our work deepens the understanding of the energetics of polymer:NFA blends and offers a basis for achieving efficient NFA properties.Reference[1] Y. Shimata, A. Saeki, J. Phys. Chem. C 121 (2017) 18351.[2] F. Hamada, A. Saeki, ChemSusChem 14 (2021) 3528.[3] S. Li, F. Hamada, R. Nishikubo, A. Saeki, Sustainable Energy Fuels 6 (2022) 756.