Structure control is widely admitted as a feasible strategy to restrain volume change and enhance electrical conductivity for chalcogenide anode materials. Herein, three-dimensionally hierarchical structure Co0.85Se@N-doped graphene hybrid is well-designed and synthesized by a facile hydrothermal strategy and post-calcination. It is noted that, owing to the nanoscale Kirkendall effect, the Co0.85Se nanograins derived from uniform zeolitic imidazolate framework (ZIF-67) precursor are incorporated into a polyhedron-in-polyhedron structure, which is consisted of in-situ formed amorphous carbon and interconnected pliable graphene nanosheets with enormous N-doping atoms. This unique dual-carbon protecting layers are beneficial to mitigate the volume expansion with high integrity, and facilitate the fast Li/electron transport with improved conductivity simultaneously, thus resulting in the superior Li-storage performance. As expected, the framework-controlled Co0.85Se@N-doped rGO composite demonstrates an outstanding cycling stability (787.7 mA h g(-1) after 1000 cycles at 2 A g(-1)) and remarkable rate capability (400.8 mA h g(-1) at ultrahigh rate of 10 A g(-1)). This work presents an enlightened strategy to design chalcogenide anode with desired nano-/microstructure by structure control and kinetic increase. (C) 2020 Elsevier Inc. All rights reserved.