Hierarchical porous carbon shows great potential for volatile organic compounds (VOCs) removal due to its high surface area and abundant porous framework. However, current fabrication protocols are complex and cause secondary pollution, limiting their application. Here, as a novel strategy, microbial lignocellulose decomposition as a pretreatment was introduced to fabricate hierarchical porous carbon (M-AC) from crude biomass substrate. The M-AC samples had high specific surface areas (maximum: 2290 m2·g-1) and surfaces characterized by needle-like protrusions with a high degree of disorder attributed to hierarchical porous structures. Dynamic toluene adsorption indicated that the carbon materials with microbial pretreatment had much better adsorption performances (maximum: 446 mg/g) than activated carbon without pretreatment. The M-AC material pretreated with a cellulose-degrading microbe showed the best adsorption capacity due to well-developed micropores, whereas the M-AC material pretreated with a lignin-degrading microbe showed excellent transport diffusion due to well-developed mesopores. Therefore, this simple and effective approach using microbial decomposition pretreatment is promising for the development of hierarchical porous carbons with adjustable pore structures and high specific surface areas to remove target VOCs in practical applications.