A technique for poly-3-hydroxybutyrate (P(3HB)) extraction with safer, non-chlorinated solvents, was developed, aiming to attain high recovery yields and purities. A wide range of solvents was selected from the GlaxoSmithKline guide as sustainable industrial solvents and the solubility of P(3HB) on those solvents calculated using predictive equations from literature. Anisole, * Corresponding author: Tel.: +351 21 8419137; Fax: +351 21 8419062. e-mail address: teresa.cesario@tecnico.ulisboa.pt + Current address: Politecnico di Milano, Dipartimento di Chimica Materiali e Ingegneria Chimica "Giulio Natta". Via Mancinelli, 7 -20131 Milano MI 2 cyclohexanone and phenetole were used as extraction solvents and the relevant process variables (extraction temperature, extraction time and mass of cells/solvent volume ratio) were optimized.Polymer recovery yields of 97% and 93% were obtained with anisole and cyclohexanone, respectively, at 120-130°C using a cell/solvent ratio of 1.5% (w/v). Maximum polymer purities using these experimental conditions were 98% for both solvents. Recovery yields and polymer purity attained with chloroform (reference solvent) were 97 and 98%, respectively. Higher cell/solvent ratios of 6.0 % (w/v) showed slightly lower recovery yields and purities The average molecular weight and the thermal properties of the polymers extracted with the alternative solvents were comparable to those of the polymers obtained by chloroform extraction, showing that the applied conditions did not significantly alter the properties of the extracted P(3HB).