Flexible poly(vinyl chloride) (fPVC) composites undertake potential high fire and smoke hazards. Withal, commercial flame retardant, antimony trioxide (Sb2O3), in application to fPVC is proved to be harmful anyhow. Meanwhile, corrosive HCl gas evolves inevitably from fPVC during combustion. In this article, mesoporous SnO2/Ca2P2O7 hybrid crystals with high specific surface area and pore volume was firstly synthesized via a facile way by utilization of the chelating resin as the precursor. The composition and structure of the hybrid material were characterized by X-ray diffraction, scanning electron microscope/transmission electron microscope coupled with energy dispersive X-ray detector and N-2 sorption isotherms. The results from limiting oxygen index, vertical burning test and cone calorimeter showed that the synthesized product reduced the fire and smoke hazards of fPVC and decreased the amount of HCl gas emission due to the combined impact of SnO2 and Ca2P2O7. Moreover, this novel flame retardant holds great potential to replace antimony trioxide and provides the promising manner to develop Sb2O3-free environmental friendly fPVC composite with low fire hazards. (C) 2017 Elsevier B.V. All rights reserved.