Abstract As the traditional anode material of lithium-ion batteries, tin dioxide (SnO2) has the characteristics of a high theoretical capacity and stable crystal structure. However, the alloying/de-alloying reaction between tin and lithium ions causes volume expansion and continuously generates an SEI film, which causes the electrode to fall off the current collector and the capacity fade rapidly. Generally, a composite of carbon materials and SnO2 can alleviate the expansion and pulverization phenomena. However, the microstructure of carbon materials is complex and changeable, which makes it difficult to definitively state the influence mechanism of the microstructure on the lithium storage performance of composite materials. Here, three kinds of lignin-based porous carbons (LPCs) with different microstructural characteristics, along with a high graphitization, high specific surface area and hierarchical porosity, are obtained by regulating the process of gas exfoliation and in situ activation. Furthermore, a series of LPC/SnO2 composites are obtained by an ultrasonic dispersion and ball milling method. Electrochemical property results show that the hierarchical porous LPCs are more conducive to the dispersion/coating of SnO2 nanoparticles and that the reversible specific capacity of the electrode material increases from 64 to 620 mA h g−1, effectively mitigating the expansion and pulverization of SnO2 during the lithium storage process.