The invention discloses a nano protective material having a synergistic function and a preparation method of the protective material, and belongs to the technology of the preparation of a protective material. The nano protective material consists of a detoxifying functional layer, a non-woven fabric, a flame-retarding functional layer and a barrier layer; the detoxifying functional layer is composed of such nano-scale photocatalytic antibacterial agents as Ag, TiO2, ZnO and the like and amino-containing nano fibers, the flame-retarding functional layer is composed of graphene and a fire retardant, and the barrier layer is composed of fluorine-containing super-hydrophobic nanofibers, wherein the non-woven fabric is a supporting layer; the detoxifying functional layer is sprayed on the lower part of the non-woven fabric; the flame-retarding functional layer is spun on the upper part of the non-woven fabric supporting layer; and the super-hydrophobic nanofiber barrier layer is sprayed on the upper part of the flame-retarding functional layer. The nano protective clothing structure of the composite structure obtained from the technical scheme shows excellent service performances in such aspects as bacterium resistance, detoxification, self-purification, flame-retarding and grease-proofing, water-proofing and the like.