Multiwalled carbon nanotube (MWCNT) cryogels were fabricated with aligned and non-aligned porous structures. The MWCNT cryogels contained a major fraction of MWCNTs with a minor fraction of silk fibroin as the structure binder. The morphology of the porous structures was controlled using a sol-gel process of silk fibroin to form the network structures. Microchannel structures were formed by ice-templating. The MWCNT cryogels contained mesopores and formed as monoliths. The MWCNT cryogels with aligned porous structures showed better thermal stability and electrical conductivity than the MWCNT cryogels with non-aligned porous structures due to the advantageous MWCNT interconnections. The morphology of the porous structures was examined by field emission scanning electron microscopy and transmission electron microscopy. The structure-property relationships of the MWCNT cryogels and the performance of the MWCNT cryogels as electrodes were investigated. (C) 2009 Elsevier Ltd. All rights reserved.