To study the catalytic depolymerization process of alkali lignin by organic bound sodium in supercritical ethanol, the solid chars and liquid oils products were first prepared by using a high pressure autoclave at different temperatures and times. The properties of solid chars then were analyzed by elemental analysis, FT-IR, and SEM, and the composition of liquid oils was characterized by GC-MS. FT-IR and SEM results showed that the depolymerization process of alkali lignin catalyzed by organic bound sodium in sub- and supercritical ethanol formed different micrometer-sized spheres products, and the sphere size of the char products was obviously affected by the depolymerized temperature. The C/O and C/H ratios of the chars products also increased with depolymerized temperature increasing. GC-MS results indicated that the components of liquid oils obtained from sub- and supercritical ethanol mainly were ester and phenolic compounds, respectively.