The invention relates to a fire-proofing and heat-insulating composite fabric with second order phase transition temperature limit, and a preparation method and application thereof. The composite fabric is composed of a heat reflection layer, two phase transition temperature limit layers, and an interval composite heat-insulating layer, which are at a right side, and a fire-retardant composite layer at a back side; and the layers are arranged in a laminated structure. When the right side of the composite fabric is effected by an open fire strong heat flow environment, the back side can maintain a safe temperature state close to human skin below 50 DEG C; and the whole fabric morphology and mechanical property are stable. The composite fabric has a natural thickness of 5-15mm, a compaction thickness of 3-8mm and weight per square meter of 400-1500g / m<2>, and is a completely closed, adhesive, sewed fire-proofing and heat-insulating fabric. The composite fabric can be used for individual protection and environment heat insulation in special high-temperature occasions, such as fire protection, military, adventure, safe escape and industry.