An efficient method for the synthesis of a self-supporting carbon framework (denoted Gra-GC-MoSe 2 ) is proposed with a triple-gradient structure-in sodiophilic sites, pore volume, and electrical conductivity-which facilitates the highly efficient regulation of Na deposition. In situ and ex situ measurements, together with theoretical calculations, reveal that the gradient distribution of Se heteroatoms in MoSe 2 , and its derivatives tailor the sodiophilicity, while the gradient distribution of porous nanostructures homogenizes the Na + diffusion. Therefore, Na deposition occurs from the bottom to the top of the Gra-GC-MoSe 2 framework without dendrite formation. In addition, the gradient in electrical conductivity ensures the stripping process does not lead to dead Na. As a result, a Gra-GC-MoSe 2 modified Na anode (Na@Gra-GC-MoSe 2 ) shows impressive cycling stability with a high average Coulombic efficiency in an asymmetric cell. In symmetric cells, it also exhibits a long cycling life of 2000 h with a low polarization voltage and works stably even under a large capacity of 10 mAh cm -2 . Moreover, a Na@Gra-GC-MoSe 2 || Na 3 V 2 (PO 4 ) 3 full cell delivers a high energy density with an excellent cycling performance.