A series of binary blends of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and polytetrahydrofuran (PTHF), characterized by similar average molecular weights, with selected fatty acids (capric acid, lauric acid, myristic acid, patmitic acid, and stearic acid) were prepared by melt mixing. Differential scanning calorimetry was applied to characterize the phase transitions of melting and crystallization, and a synergistic effect was found to occur for PEO/fatty acid blends, as evidenced by the values of the enthalpy of the phase transition. This effect vas probably due to hydrogen bonding between PEO and the fatty (carboxylic) acids, which facilitated the formation of crystalline structures; an analysis of IR spectroscopy data showed a shift in the absorption bands of OH groups. The morphology development of the PEO/carboxylic acid blends, as observed with polarizing light microscopy, could be described as spherulitic growth with spontaneous selection of the lamellar thickness. The textures of the individual fibrils, consisting of stacks of several tens of lamellae corresponding to PPO and PTHF, were less regular than the texture of PEO and showed large macroscopic heterogeneity. (C) 2003 Wiley Periodicals, Inc.