Morphological characterization of polymer blends is important for tailoring final properties of plastic products based on these systems. A novel technique to estimate the characteristic dimension and size distribution of a polymer blend is proposed and tested. The procedure is based on Fourier transform rheology (FTR) and large-amplitude oscillatory shear experiments and exploits their sensitivity to microstructural properties. The inference protocol requires that the experimental data are analyzed with a model capable of describing the blend dynamics. This novel technique is applicable to immiscible polymer blends of practical industrial interest. The procedure is successfully tested on a model system (an immiscible polymer blend of PDMS in PIB) by treating the polymer blends with the Maffettone–Minale model coupled with the Batchelor theory.