Polyfluorene-based polymer blends have been utilized in the development of optoelectronic devices. The constituent copolymers are chemically designed to facilitate more efficient electron/hole mobility, thereby enhancing control over exciton formation and dissociation. When appropriate pairs of these are blended together, intermolecular charged-particle localizations are induced, leading to significant intermolecular charge-transfer character and luminescence that exhibit some sensitivity to their interfacial orientation. The authors report on a time-dependent density functional theory quantum chemical investigation of the relevant excited states of the polymer blend poly[9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine]/poly(9,9-dioctylfluorene-co-benzothiadiazole. They show that the calculated excited states generally agree with experimental observations although there is a consistent underestimation of the charge-transfer states. Further, they show sensitivity to lateral shifts in interfacial stacking. Finally, solvation with a low dielectric solvent greatly stabilizes the charge-transfer states.