Pine wood was pretreated with H2SO4 and NaOH, followed by liquefaction in methanol at temperatures ranging from 200 to 350 °C, to produce bio-oil. Composition analysis and scanning electron microscopy (SEM) observation were performed to study the impact of the pretreatment on the pine wood structure. The SEM images showed that the structures of the samples were destroyed by pretreatment. After being pretreated by H2SO4, the size of holes generated was smaller than that with pretreatment by NaOH. Furthermore, the influences of the temperature, methanol content, and residence time on the yield of the water-soluble fraction (WS), ether-soluble fraction (ES), and bio-oil were determined. Shorter residence time and higher amounts of methanol favored the products of WS, ES, and bio-oil. Gas chromatography-mass spectrometry (GC-MS) analysis showed that phenols, ketones, aromatics, and aldehydes are the main components of bio-oil.