α and β crystalline phases of poly(ethylene furanoate) (PEF) were determined using X-ray powder diffraction by structure resolution in direct space and Rietveld refinement. Moreover, the α’ structure of a PEF sample was refined from data previously reported for PEF fiber. Triclinic α-PEF a = 5.729 Å, b = 7.89 Å, c = 9.62 Å, α = 98.1°, β = 65.1°, γ = 101.3°; monoclinic α’-PEF a = 5.912 Å, b = 6.91 Å, c = 19.73 Å, α = 90°, β = 90°, γ = 104.41°; and monoclinic β-PEF a = 5.953 Å, b = 6.60 Å, c = 10.52 Å, α = 90°, β = 107.0°, γ = 90° were determined as the best fitting of X-ray diffraction (XRD) powder patterns. Final atomic coordinates are reported for all polymorphs. In all cases PEF chains adopted an almost planar configuration.