Hierarchical porous carbon aerogel with a continuous three-dimensional framework has been synthesized via evaporation induced, coassembly based sol gel polymerization of organic and inorganic precursors, for application as the anode in a Li-ion battery. A combination of resorcinol (R) and formaldehyde (F) as organic precursors and hybrid silica sources composed of TEOS (tetraethyl orthosilicate), APTES (3-aminopropyl triethoxysilane) and APTEMS (3-aminopropyl trimethoxysilane) as inorganic precursors has been used to obtain the porous carbon monolith. The porosity of the carbon aerogel has been tuned by varying the ratio of APTES/APTEMS. Postpyrolysis, the etching of the composite to remove silica network resulted in the formation of a high specific surface area (BET similar to 2600 m(2) g(-1)) carbon containing the distribution of micro-, meso-and macroporous domains. The electrode exhibits a high reversible capacity of 890 mAh g 1 after 100 cycles at a current density of SO mA g(-1).