As a nutrient in body functions, folic acid (FA) plays a very important role for human health, thus developing highly sensitive method for its determination is of great significance. In the present work, hollow carbon nanospheres decorated with molybdenum disulfide nanosheets (CHN@MoS2) nanomaterials were produced through a simple method and adopted to modify glassy carbon electrode for assembling a highly sensitive electrochemical sensor of FA. After characterizing the prepared nanomaterials using scanning-/transmission-electron microscopy and Raman spectra as well as optimizing various testing conditions including pH value of buffer solution, accumulation time and amount of nanomaterials on electrode surface, the electrochemical determination of FA was carried out using CHN@MoS2 electrode. Owing to the coordinative advantages from CHN and MoS2, the results show that CHN@MoS2 exhibits excellent sensing responses for FA, and it has wide linear range from 0.08 to 11.0 μM coupled with a low detection limit of 0.02 μM. Finally, the proposed method for FA detection was applied successfully in human serum analysis and the obtained results are satisfactory, revealing the developed method based on CHN@MoS2 nanomaterials has important applications for FA determination.