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Abstract: Temperature dependence on the phase structure was investigated for drawn and undrawn ultrahigh molecular weight polyethylene (UHMWPE) by solid-state high resolution 13C NMR. The fully relaxed DD/MAS 13C NMR spectra provided the fractions of crystalline, interphase, and amorphous, and the analysis on molecular mobility by spin-lattice relaxation time provided three components in the orthorhombic phase, two components in the monoclinic phase and a single component in the interphase and amorphous phase, respectively. The molecular mobility of orthorhombic phase for drawn UHMWPE was the lowest of three samples, corresponding to the most rigid. This closely relates with good mechanical properties for drawn UHMWPE. The T1C was as high as 2040 s even at 100 °C for drawn UHMWPE. With increasing temperature, a part of the most mobile chain in the orthorhombic phase which locates at the lamellar surface transforms to that in the interphase, and then the interphase also transforms to the amorphous. The drawn UHMWPE had high fraction of the monoclinic phase and lattice defect which are induced by highly drawing. These fractions decreased with increasing temperature. So the monoclinic phase exists as a defect in the orthorhombic phase, and the molecular chain corresponding to the lattice defect would connect the monoclinic and orthorhombic phases. The monoclinic phase transforms to the orthorhombic phase with increasing temperature. This resulted in the small fractional decrement of orthorhombic phase.