Blends of poly(ethylene oxide) (PEO) and novolac type phenolic resin were prepared by a solution cast method using acetonitrile as a solvent. In this work, we have investigated the PEO/phenolic blends having low phenolic content (0 to 30 wt %) with the objective in mind to design a crystallizable component for a shape memory polymer system having adjustable switching temperature. The blends were characterized by Fourier transform infrared (FTIR) spectroscopy, polarized optical microscopy (POM), and differential scanning calorimetry (DSC). The rate of crystallization and crystallinity (calculated from heat of crystallization value) decrease with increase in novolac content. FTIR analysis indicates the existence of H-bonding between hydroxyl groups of novolac and ether groups of PEO. POM studies indicate that size of Maltese cross section decreases with increase in novolac content and in the blends containing higher novolac content less regular leaf like texture was obtained. (C) 2008 Wiley Periodicals, Inc.