Modification of electrospun nanofibrous poly(3-hydroxyalkanoate) (PHA)-based mats was implemented through two routes to obtain biomimetic scaffolds meant for tissue engineering applications. The first strategy relied on a physical functionalization of scaffolds thanks to an original route which combined both electrospinning and electrospraying, while the second approach implied the chemical modification of fiber surface via the introduction of reactive functional groups to further conjugate bioactive molecules. The degree of glycidyl methacrylate grafting on PHA reached 20% after 300 s under photoactivation. Epoxy groups were modified via the attachment of a peptide sequence, such as Arg-Gly-Asp (RGD), to obtain biofunctionalized scaffolds. SEM and TEM analysis of mats showed uniform and well-oriented beadless fibers. The electrospinning/electrospraying tandem process afforded highly porous scaffolds characterized by a porosity ratio up to 83% and fibers with a surface largely covered by the electrosprayed bioceramic, i.e. hydroxyapatite. Gelatin was added to the latter PHA -based scaffolds to improve the hydrophilicity of the scaffolds (water contact angle about 0 degrees) as well as their biological properties, in particular cell adhesion, proliferation, and osteogenic differentiation after 5 days of human mesenchymal stromal culture. Human mesenchymal stromal cells exhibited a better adhesion and proliferation on the biofunctionalized scaffolds than that on non-functionalized PHA mats. (C) 2016 Elsevier B.V. All rights reserved.