In order to enlarge the utilization field of wood and decrease the costs of carbon fibers, carbon fiber precursors from liquefied wood were prepared by soaking liquefied wood in a solution containing hydrochloric acid and formaldehyde, after melt-spinning by adding hexamethylenetetramine. The microstructure evolution of the precursor during carbonization was studied by FTIR, X-ray analysis and Raman spectroscopy. The results show that precursors from liquefied wood above 400°C had diffraction peaks corresponding to the (100) crystal plane. When the carbonization temperature reached 500°C, Raman spectroscopy showed the D peak at wave number of 1360 cm−1 and the G peak at 1595 cm−1. By increasing the carbonization temperature, the microstructure of the precursors became more ordered. Although the structure of the precursor changed at 500 and 800°C, the peaks at 1632 and 1454 cm−1 corresponding to the characteristic vibrations of aromatic rings, remained during carbonization. This implies that the precursor from liquefied wood cannot be easily formed into graphite.