Ultrahigh molecular weight polyethylene was investigated using in situ confocal micro-Raman spectroscopy during annealing at 110.0°C. Based on the Raman spectra, crystalline, amorphous, and all-trans noncrystalline fractions were recognized to evaluate rearrangement kinetics during isothermal annealing at 110.0°C and phase evolution during cooling from 110.0 to 30.0°C. For the crystalline fraction, a substantial increase from 0.600 ± 0.001 to 0.639 ± 0.008 was observed during the first 24.2 min of annealing; a very gradual increase from 0.639 ± 0.001 to 0.679 ± 0.001 occurred during the following 114.6 min. For the amorphous phase fraction, conversely, a sharp decrease from 0.240 ± 0.000 to 0.213 ± 0.004 was exhibited during the first 24.2 min of annealing, and then, a flat decrease happened from 0.213 ± 0.004 to 0.192 ± 0.001 as time expanded to 138.8 min. For the all-tans noncrystalline fraction, a gradual decrease was shown from 0.160 ± 0.000 at 0.0 min to 0.128 ± 0.001 at 138.8 min. The rearrangement rate constant K was obtained to be 0.632 by an Avrami equation. During cooling from 110.0 to 30.0°C, there were two phase evolution regions: region 1 from 110.0 to 90.0°C and region 2 from 90.0 to 30.0°C. The crystal lamella thickened faster in region 1 than in region 2. The amorphous layer continually decreased in content in the combined region of 1 and 2. The all-trans noncrystalline phase obviously decreased in region 1 and then almost maintained a constant level in region 2.