Poly(3-hydroxyalkanoate)s PHAs have been demonstrated to be a family of biopolyester with good biodegradability and biocompatibility. A glycosaminoglycan-like marine exopolysaccharide EPS HE800 was here incorporated to enhance cell adhesion. Novel graft copolymer HE800-g-PHA were prepared to improve the compatibility between hydrophobic PHA and hydrophilic HE800. The carboxylic end groups of PHA oligomers were activated with acyl chloride functions, allowing coupling to hydroxyl groups of HE800. Fibrous scaffolds were prepared by a modified electrospinning system which combined simultaneously PHA electrospinning and HE800-g-PHA copolymer electrospraying. Adhesion and growth of human mesenchymal stem cells on the HE800-g-PHA scaffolds showed a notable improvement over those on PHAs matrices. (C) 2012 Elsevier Ltd. All rights reserved.