A facile one‐step spraying synthesis of MoS₂/C microspheres and their enhanced electrochemical performance as anode of sodium‐ion batteries is reported. An aerosol spraying pyrolysis without any template is employed to synthesize MoS₂/C microspheres, in which ultrathin MoS₂ nanosheets (≈2 nm) with enlarged interlayers (≈0.64 nm) are homogeneously embedded in mesoporous carbon microspheres. The as‐synthesized mesoporous MoS₂/C microspheres with 31 wt% carbon have been applied as an anode material for sodium ion batteries, demonstrating long cycling stability (390 mAh g⁻¹ after 2500 cycles at 1.0 A g⁻¹) and high rate capability (312 mAh g⁻¹ at 10.0 A g⁻¹ and 244 mAh g⁻¹ at 20.0 A g⁻¹). The superior electrochemical performance is due to the uniform distribution of ultrathin MoS₂ nanosheets in mesoporous carbon frameworks. This kind of structure not only effectively improves the electronic and ionic transport through MoS₂/C microspheres, but also minimizes the influence of pulverization and aggregation of MoS₂ nanosheets during repeated sodiation and desodiation.