We aimed to develop a non-toxic and simple recovery procedure for poly(3-hydroxybutyrate) based on the use of green solvent. In this study, 2-methyltetrahydrofuran, 1,3-propanediol, 1,3-dioxolane and ethyl lactate were investigated and compared with chloroform in the extraction of poly(3-hydroxybutyrate) from Cupriavidus necator strain A-04. A water-miscible system was developed using 1,3-dioxolane and water. PHB was extracted from dried cells at 80 degrees C for 6 h in 1,3-dioxolane then water was used to cause phase separation of PHB film from 1,3-dioxolane solution resulted in the recovery yield 92.7% +/- 1.4% and purity up to 97.9% +/- 1.8%. The physical properties and molecular weight distribution of the PHB recovered were not significantly affected by the 1,3-dioxolane extraction. The PHB obtained from wet cells by 1,3-dioxolane extraction at 80 degrees C for 6 h had a M-W of 4.86 x 10(5), MN of 3.74 x 10(5), polydispersity index of 1.30. The recovery process is non-toxic and very simple, thus reducing purification costs.