With a high melting temperature and good crystallization ability, poly(neopentyl glycol 2,5-furandicarboxylate) (PNF), a polyester derived from bio-based 2,5-furandicarboxylic acid and neopentyl glycol, has been proposed and proved to be a promising hard segment for the development of novel bio-based thermoplastic poly(ether-ester) elastomer (TPEE). The resulting TPEE, namely PNF-PTMG, has high performance comparable to the petroleum-based counterpart PBT-PTMG (i.e., Hytrel, Dupont). Among all of the existing polyesters derived from bio-based 2,5-furandicarboxylic acid (FDCA), PNF has perfectly balanced properties, namely, a high melting temperature of 200 degrees C and a good crystallization ability to easily grow medium to large-size crystalline spherulites. Characterizations based on dynamic mechanical analysis and small-angle X-ray scattering suggest that there are two domains in PNF-PTMG, the crystalline PNF and a mixture of amorphous PNF and PTMG. These two domains form microphase separation induced mainly by the crystallization of PNF. By adjusting the PTMG soft segment from 30 to 60 wt%, PNF-PTMG shows a melting temperature, tensile modulus (E), and elongation at the break (epsilon(b)) ranging from 180 to 134 degrees C, 738 to 56 MPa, and 38 to 1089%, respectively. More importantly, the shape recovery ratios increase from 57 to 90% at 200% strain when the amount of PTMG increases from 50 to 70 wt%, indicating excellent elastic property. These results indicate that PNF is an excellent hard segment to serve as a strong physical cross-link so that PNF-PTMG is able to display high performance comparable to extensively commercialized PBT-PTMG.