The mechanical and electrical characteristics of films, buckypapers and fiber materials from combinations of clay, carbon nanotubes (CNTs) and chitosan are described. The rheological time-dependent characteristics of clay are maintained in clay-carbon nanotube-chitosan composite dispersions. It is demonstrated that the addition of chitosan improves their mechanical characteristics, but decreases electrical conductivity by three-orders of magnitude compared to clay-CNT materials. We show that the electrical response upon exposure to humid atmosphere is influenced by clay-chitosan interactions, i.e., the resistance of clay-CNT materials decreases, whereas that of clay-CNT-chitosan increases.