Nitrogen-doped aligned CNT/graphene sandwiches are rationally designed and in-situ fabricated by a facile catalytic growth on bifunctional natural catalysts that exhibit high-rate performances as scaffolds for lithium-sulfur batteries, with a high initial capacity of 1152 mA h g(-1) at 1.0 C. A remarkable capacity of 770 mA h g(-1) can be achieved at 5.0 C. Such a design strategy for materials opens up new perspectives to novel advanced functional composites, especially interface-modified hierarchical nanocarbons for broad applications.