Hydrolysis and alcoholysis are considered as viable routes for efficient degradation and recycling high-quality gas fuel of lignin. Mechanism of formation H2 and CH4 by hydrolysis and alcoholysis of various phenylic lignin model compounds were studied using density functional theory method at M06–2X/6–31++G(d,p) level. Formation H2 by eight hydrolysis reaction pathways and formation CH4 by eight alcoholysis reaction pathways were designed. The standard kinetic and thermodynamic parameters of hydrolysis and alcoholysis reaction pathways were calculated. The results show that energy barriers for hydrolysis of phenyl (p-hydroxyphenyl, guaiacyl, and syringyl) formaldehyde paths (about 270.0 kJ/mol) are higher than those for hydrolysis of phenyl (p-hydroxyphenyl, guaiacyl, and syringyl) acetaldehyde paths (about 250.0 kJ/mol). Thus, H2 is easily formed during the decomposition of phenyl (p-hydroxyphenyl, guaiacyl, and syringyl) acetaldehyde. The energy barriers for alcoholysis of phenyl (p-hydroxyphenyl, guaiacyl, and syringyl) formaldehyde paths (about 370.0 kJ/mol) are lower than those for alcoholysis of phenyl (p-hydroxyphenyl, guaiacyl, and syringyl) acetaldehyde paths (about 355.0 kJ/mol). Thus, CH4 is easily formed during the decomposition of phenyl (p-hydroxyphenyl, guaiacyl, and syringyl) acetaldehyde. In addition, temperature is the key factor in the lignin degradation process, the calculation results indicate the reaction rate increases with the increase of temperature, and the reaction in water molecular environment is better than that in methanol medium.