A kind of hierarchical porous carbon (HCN) with three-dimensional network frameworks was successfully prepared by solvent-free nanocasting method using glucose as carbon source and ordered MCM-41 type of mesoporous silica with the different particle sizes as template. Meanwhile, its structure features and texture parameters were characterized by using XRD, N-2 adsorption-desorption isotherms, SEM and TEM, FT-IR, Raman spectrum, XPS techniques. These results demonstrated that during the process of pyrolysis glucose was strongly interacted with mesoporous silica, leading to effective loading, then inverse duplicated the structure of mesoporous silica. The obtained sequence of hierarchical porous carbons possessed well-interconnected network structure and tunable wall thickness and size of network macropore. As demonstrations, the capacity of absorbed CO2 for serials of hierarchical porous carbons with three-dimensional network frameworks under room temperature was investigated. The result of CO2 adsorption isotherms indicated that the HCN pore architecture and morphologies played a key role in the CO2 capture process, specifically the size of network macropore and thickness of macroporous wall significantly affected the textural structure, the high microporous contents were benefit with improving the capacity of absorbed CO2.