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Enhanced scattering contrast afforded by resonant soft X-ray scattering (R-SoXS) is used to probe the nanomorphology of all-polymer solar cells based on blends of the donor polymer poly(3-hexylthiophene) (P3HT) with either the acceptor polymer poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2′,2″-diyl) (F8TBT) or poly([N,N′-bis(2-octyldodecyl)-11-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-12-bithiophene)) (P(NDI2OD-T2)). Both P3HT:F8TBT and P3HT:P(NDI2OD-T2) blends processed from chloroform with subsequent annealing exhibit complicated morphologies with a hierarchy of phase separation. A bimodal distribution of domain sizes is observed for P3HT:P(NDI2OD-T2) blends with small domains of size ∼5–10 nm that evolve with annealing and larger domains of size ∼100 nm that are insensitive to annealing. P3HT:F8TBT blends in …