In this work, a novel pyrrolic nitrogen-doped carbon sandwiched monolayer MoS2 hybrid was prepared. This sandwiched hybrid vertically anchors on graphene oxide as anode materials for sodium-ion batteries. Such electrode was fabricated by facile ionic liquid-assisted reflux and annealing methods. Owing to rational structure and enhancement from pyrrolic nitrogen dopant, this unique MoS2/C-graphene hybrid exhibits reversible specific capacity of 486 mAh g−1 after 1000 cycles with a low average fading capacity of 0.15 mAh g−1 (fading cyclic rate of ca. 0.03% per cycle). A capacity of 330 mAh g−1 is remained at the current densities of 10.0 A g−1. The proposed strategy provides a convenient way to create new pyrrolic nitrogen-doped hybrids for energy field and other related applications.