Free volume properties of a series of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) membranes, which were produced by various nonisothermal crystallization processes (rapid-, step-, and slow-cooling processes), were investigated using positron annihilation lifetime (PAL) spectroscopy Over a temperature range of 25-90 degrees C. From the annihilation lifetime parameters, the temperature dependence of free volume size, amount, size distribution, and fractional free volume and thermal expansion properties of free volume were discussed. A model which assumed that amorphous phase was subdivided into mobile and rigid amorphous fractions (MAF and RAF) in the semicrystalline polymer was considered to interpret the temperature dependence of those free volume properties. Morphological observation of the Semi-crystalline polymer by small-angle X-ray scattering (SAXS) indicated that the rapid-cooled (cold-crystallized) membranes showed a much thinner thickness of the repeating lamellar/amorphous layers and most likely higher amount of RAF, which restrained the chain motion, than the step- and slow-cooled (melt-crystallized) membranes. The difference of free volume properties among various PHBV membranes was created according to the crystalline structure of the polymer from different thermal history. The polymer crystallized with slower cooling rate induced higher crystallinity and resulted in less free volume amount and lower fractional free volume. In addition, the thermal expansion coefficients of free volume size were affected by the crystallization rate of PHBV polymer. Larger distribution of the free volume size of melt-crystallized membranes was observed as a result of the bimodal distribution of the lamellar periodicity and less amount of RAF than that of the cold-crystallized membranes. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 855-865, 2009