This invention relates to rigid porous carbon structures and to methods of making same. The rigid porous structures have a high surface area which are substantially free of micropores. Methods for improving the rigidity of the carbon structures include causing the nanofibers to form bonds or become glued with other nanofibers at the fiber intersections. The bonding can be induced by chemical modification of the surface of the nanofibers to promote bonding, by adding "gluing" agents and/or by pyrolyzing the nanofibers to cause fusion or bonding at the interconnect points.