In order to valorize lignin wastes to produce useful aromatic compounds, the thermal degradation pyrolysis of Kraft lignin in the absence of catalysts has been investigated at 350, 450, and 550 °C. The high content of sulfur in the fresh sample led to the formation of S-containing compounds in products whose evolution in the gas phase was monitored through GC-MS analysis. Pyrolytic gas is rich in CH4, CO, CO2, and H2S with the presence of other sulfur compounds in smaller amounts (i.e., CH3SH, CH3-S-CH3, SO2, COS, and CS2). Biochar morphology and elemental composition have been investigated by means of SEM and EDX. The carbon content reaches ~90% after pyrolysis at 550 °C, while the oxygen content showed a decreasing trend with increasing temperature. From GC-MS analysis, bio-oil resulted rich in alkyl-alkoxy phenols, together with (alkyl)dihydroxy benzenes and minor amounts of hydrocarbons and sulfur compounds. NaOH/H2O and EtOH/H2O extraction were performed with the aim of extracting phenolic-like compounds. Sodium hydroxide solution allowed a better but still incomplete extraction of phenolic compounds, leaving a bio-oil richer in sulfur.