A dendritic morphology, induced by miscibility with strong intermolecular interaction between poly(ethylene oxide) (PEO) and bioresourceful tannin [tannic acid (TA)]. Mechanism was investigated by differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy, wide-angle X-ray diffraction, and polarized optical microscopy. The cell crystallography preference in correlation to the intermolecular interaction in the dendrites in PEO/TA (70/30) blend was analyzed. Dendritic morphology was more distinct at PEO/TA = 70/30 composition, where the spherulitic growth rate showed a highly nonlinear relationship with respect to crystallization time (R alpha t (1/2)). Diffusion limitation mechanism caused by the crystallography preference attributed to the strong intermolecular interaction between PEO and TA was at work.