To improve the thermal properties of softwood soda lignin, we studied a method of lignin modification using black liquor powder and polyethylene glycol (PEG). In this process, the black liquor powder was directly treated with PEG under alkaline conditions to produce a thermal melting material (alkaline PEG treatment). A model experiment was performed to determine the reaction of the lignin. The lignin in the black liquor powder consisted of 62.16% acid-insoluble lignin (purified lignin) and 37.84% acid-soluble lignin. After alkaline PEG treatment using purified lignin, the samples exhibited weak thermal melting during softening point analysis but did not exhibit appropriate thermal melting during thermal mechanical analysis (TMA). Nuclear magnetic resonance (NMR) data suggest that there was no linkage between lignin and PEG in the alkaline PEG-treated lignin prepared from the purified lignin. On the other hand, when using acid-soluble lignin, NMR data suggest that PEG was introduced to the lignin at its α-carbon position. Acid-soluble lignin PEG derivatives could work as plasticizers to induce the thermal melting of the alkaline PEG-treated lignin prepared from black liquor powder.