Poly(ethylene 2,5-furandicarboxylate) (PEF) is regarded as a bio-based alternative or complementary polyester for the widely used fossil resource-based polyester, poly(ethylene terephthalate) (PET). High-speed melt spinning of PEF of low and high molecular weight (L-PEF, H-PEF) was conducted, and the structure and properties of the resultant as-spun fibers were investigated. The occurrence of orientation-induced crystallization was confirmed for the H-PEF at the take-up velocity of 6.0 km/min, the highest speed for producing PET fibers in the industry. Molecular orientation and crystallinity of the as-spun fibers increased with the increase of take-up velocity, where the H-PEF fibers always showed a higher degree of structural development than the L-PEF fibers. The tensile modulus of the high-speed spun H-PEF fibers was relatively low at 5 GPa, whereas a sufficiently high tensile strength of approximately 500 MPa was measured. These values are adequately high for the application in the general semi-engineering fiber field.