In this paper, an effective flame retardant consisting of hierarchical magnesium hydrate (MH) nanosheets doped with molybdenum trioxide nanoparticles (MO@MH) was successfully synthesized via a hydrothermal process. Then, MO@MH, MH, and MH/MO were respectively incorporated into flexible polyvinyl chloride (fPVC) to prepare a series of composites via melt blending. The results of limiting oxygen index (LOI), UL-94, and cone calorimetry test showed that MO@MH exhibited better flame retardancy and smoke suppression than MH and MH/MO due to the synergistic effect of MO and MH, and the hierarchical structure of MO@MH. With the addition of 20 phr MO@MH, LOI value of fPVC was increased from 23.9% to 33.8% , and UL-94 reached V0 rating. The peak heat release rate, total heat release, peak smoke production rate, and total smoke production were decreased to 143.0 kW/m(2), 44.9 MJ/m(2), 0.0093 m(2)/s and 29.4 m(2), respectively. The thermogravimetric analysis results suggested that MO@MH greatly promoted the dehydrochlorination of fPVC at lower temperature, so that more compact and continuous char residues were formed. The Fourier transform infrared spectroscopy results indicated that MO@MH can prevent chain scission and oxidation of fPVC carbonaceous backbone, and as a result less smoke was released.