This article describes a combined experimental and theoretical study on nanophase structure development as a result of liquid phase demixing in solution-cast blends of the organic semiconductor poly(9,9'-dioctyl fluorene) (PFO) and the ferroelectric polymer poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)). Blend layers (200 nm) are prepared by spin coating a 1:9 (w/w) PFO:P(VDF-TrFE) blend solution in a common solvent on a poly(ethylenedioxy thiophene)/poly(styrene sulfonate) substrate. Owing to the pronounced incompatibility between the two polymers, a strong phase-separated morphology is obtained, characterized by disk-like nanodomains of PFO embedded in a P(VDF-TrFE) matrix, as revealed by scanning electron microscopy. By varying the processing conditions, we find the average domain size and standard deviation to increase with spinning time. The considerable increase in domain size suggests the coarsening process not to be impeded by a steep rise in viscosity. This indicates solvent evaporation to be only moderate within the experimental time frame. The evolution of the observed phase morphology is modeled using ternary diffuse interface theory integrated with a modified Flory-Huggins (FH) treatment of the homogeneous (bulk) free energy of mixing, to account for significant molecular differences between the active blend components. Using calculated FH interaction parameters, the model confirms the phase separation to occur via spinodal decomposition of the blend solution during spin coating, as suggested by experimental observations. The simulated phase morphologies as well as the modeled trends in domain growth and standard deviation compare favorably with the experimental data. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1255-1262, 2011