The increasing volume of plastic has caused the serious problem in environment. One way to solve this problem is preparation of new plastic materials which can be decomposed by microorganisms in environment These plastics may be prepared from non‐biodegradable material by modification of theirs physical and chemical properties, preparation of theirs copolymers and polyblends. The main problem in preparation of polyblends is compatibility between polymers mixtures. In this work has focused on preparation of polyblends between poly(vinyl alcohol) (PVA) and poly(ε‐caprolactone) (PCL) in various compositions by casting of polymers solution. Characterizations of polyblends were carried out by analysis of functional groups (FTIR), thermal property (DSC and TGA/DTA), mechanical properties (Tensile tester), and crystallinity (XRD). The results of polyblends showed that the compatible and homogeneous polyblends were obtained in solvent composition (dimethyl sulfoxide/tetrahydrofurane) (DMSO/THF) of 3:1 and PCL ratio in polyblends less than 15 % (w/w). The absorption intensity of carbonyl and alkyl groups observed in 1725 cm−1 and 2940 cm−1 increased with increasing PCL composition in polyblends. The melting point (Tm) and fusion enthalpy (ΔHm) for PCL region in polyblends decreased with decreasing PCL composition, but melting point (Tm) and fusion of enthalpy (ΔHm) for PVA region increased. The total fusion enthalpy value obtained by observation was smaller than that of calculation value, indicating the presence of interaction between PCL and PVA to form a part of compatible polyblends with more amorphous structure. The mechanical properties of polyblends tended to decrease with increasing PCL ratio in polyblends. These results were supported by analysis of crystallinity with using X‐ray diffraction.

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