Abstract Lignin is considered as a renewable and sustainable resource for producing value-added aromatic chemicals and functional carbon materials. Herein, we develop a one-step catalyst-free depolymerization strategy to convert lignin into aryl monomers and carbon nanospheres simultaneously. Importantly, microwave-assisted depolymerization (MAD) in conjunction with dichloromethane (CH2Cl2) vapors is developed. The total mass yield of guaiacols reached the highest amount of 225.1 mg/g at 600 °C, and the highest yields of phenols (49.0 mg/g) and aromatic hydrocarbons (155.1 mg/g) were obtained at 700 °C. Hydrogen radicals and hydrogen chloride (HCl) are in-situ formed from CH2Cl2, significantly decreasing the activation barrier and reforming pyrolysis vapors to promote the formation of aryl monomers. Interestingly, uniform carbon nanospheres with an average size of 140 nm were produced as co-products at 700 °C. The microwave “hot-spots”, allied with the continuous surface erosion and the decrease in surface energy of lignin-derived carbon precursors by CH2Cl2 vapor, can be considered the driving force for the ultimate formation of carbon nanospheres. The CH2Cl2/MAD system produces aryl monomers (26.8 wt% yield) and carbon nanospheres (36.6 wt% yield) at 700 °C. We provide a facile, intriguing and scalable approach to convert lignin to valuable aryl monomers and sustainable carbon materials that can be applied in the chemistry, energy and environmental fields.