The development of sodium-ion batteries for large-scale applications requires the synthesis of electrode materials with high capacity, high initial Coulombic efficiency (ICE), high rate performance, long cycle life, and low cost. A rational design of freestanding anode materials is reported for sodium-ion batteries, consisting of molybdenum disulfide (MoS2) nanosheets aligned vertically on carbon paper derived from paper towel. The hierarchical structure enables sufficient electrode/electrolyte interaction and fast electron transportation. Meanwhile, the unique architecture can minimize the excessive interface between carbon and electrolyte, enabling high ICE. The as-prepared MoS2@carbon paper composites as freestanding electrodes for sodium-ion batteries can liberate the traditional electrode manufacturing procedure, thereby reducing the cost of sodium-ion batteries. The freestanding MoS2@carbon paper electrode exhibits a high reversible capacity, high ICE, good cycling performance, and excellent rate capability. By exploiting in situ Raman spectroscopy, the reversibility of the phase transition from 2H-MoS2 to 1T-MoS2 is observed during the sodium-ion intercalation/deintercalation process. This work is expected to inspire the development of advanced electrode materials for high-performance sodium-ion batteries.