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In this study, a novel RGD peptide end\u2010functionalized poly(ethylene glycol)\u2010<jats:italic>b<\/jats:italic>\u2010poly(lactic acid)\u2010<jats:italic>b<\/jats:italic>\u2010poly(globalide)\u2010<jats:italic>b<\/jats:italic>\u2010poly(lactic acid)\u2010<jats:italic>b<\/jats:italic>\u2010poly(ethylene glycol) (RGD\u2010PEG\u2010PLA\u2010PGl\u2010PLA\u2010PEG\u2010RGD) is synthetized and used to prepare functional scaffolds. The PGl inner block is obtained by enzymatic ring\u2010opening polymerization of globalide. The outer PLA blocks are obtained by ring\u2010opening polymerization of both, <jats:sc>l<\/jats:sc>\u2010lactide or a racemic mixture, initiated by the <jats:italic>\u03b1<\/jats:italic>\u2010<jats:italic>\u03c9<\/jats:italic>\u2010telechelic polymacrolactone. The presence of PGl inner block enhances the toughness of PLA\u2010based scaffolds, with an increase of the elongation at break up to 300% when the longer block of PGl is used. PLA\u2010PGl\u2010PLA copolymer is coupled with <jats:italic>\u03b1<\/jats:italic>\u2010<jats:italic>\u03c9<\/jats:italic>\u2010telechelic PEG diacids by esterification reaction. PEGylation provides hydrophilic scaffolds as the contact angle is reduced from 114\u00b0 to 74.8\u00b0. That difference improves the contact between the scaffolds and the culture media. Moreover, the scaffolds are functionalized with RGD peptides at the surface significantly enhancing the adhesion and proliferation of bone marrow\u2010derived primary mesenchymal stem cells and MC3T3\u2010E1 cell lines in vitro. 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