Polymer blending is a classical approach to develop new generation materials. The investigation of material rheological and microstructure properties of the blend is essential for product development with optimized properties. In this study, poly(ethylene-co-methyl acrylate)/poly(vinylidene fluoride) (EMA/PVDF) blend prepared by melt-mixing in which PVDF concentration is varied from 10 to 40 wt%. The morphology studies of the blends using electron microscopy revealed the formation of matrix-droplet architecture. PVDF nano-droplets were dispersed in the EMA matrix, and droplet coalescence observed with the increase in PVDF concentration. The storage modulus was increased after 150 s in the time resolved modulus studies indicates the presence of specific interactions and possible physical crosslinking during the processing. Fourier transform infrared spectroscopy (FT-IR), and differential scanning calorimetry (DSC) analysis delineate the specific interactions formed during the processing. The shift in the characteristic stretching peak of the carbonyl group from 1732 to 1738 cm−1 and the formation of an exothermic peak at 100 °C during the heating cycle of the calorimetric study demonstrated the presence of the anomalies during processing. Optical microscopy and small-angle X-ray spectroscopy (SAXS) were employed to study the time resolve crystallization of EMA under isothermal condition. The increase of crystals formation with time was observed from the optical microscopy. SAXS study demonstrates that the average hard block thickness (159 Å), and the long period (134 Å) values were found maximum when the EMA samples were kept under isothermal condition at 64 °C