The blends of poly(trimethylene terephthalate) (PTT) and ethylene propylene diene monomer (EPDM) with different composition have been studied by positron lifetime technique (PLT) and differential scanning calorimetric (DSC) measurements. The DSC results for the blends of 50/50 and 40/60 show clear two glass transition temperatures indicating two-phase system. No melting point depression was observed for the blend system, which strongly supports the incompatibility. From the positron results an increase in free volume hole size and its concentration has been observed with the increase in EPDM content of the blend which indicates further that there is coalescence of free volumes of EPDM with the PTT to some extent and phase separation behavior continues. Another interesting aspect is that the relative fractional free volume exhibits neither negative nor positive deviation from the log additivity rule. It agrees well with the log additivity rule. The interchain interaction parameter evaluated from these results show some complex behavior. XRD results show the decrease in crystallinity of the blend with the increase in fractional free volume with the increase in concentration of EPDM. (c) 2005 Elsevier Ltd. All rights reserved.