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The present research reports the insulating multilayer complex based on basalt fiber and Phase Change Materials, under destructive testing and flashover conditions. Flammability and toxicity of phase change materials are discussed from molecular point of view. Single layer, basalt and fiber glass and Multilayer complex incorporated with phase change materials were study. Multilayer complex were constructed mainly by three layers with a felted punch incorporated PCMs. Differential Scanning Calorimeter (DSC), UV-vis-NIR spectroscopy, Fourier Transform Infrared (FTIR), Thermogravimetric Analysis (TGA), Air Permeability, and Flame Protective Performance Analysis (FPPAS) which is Donghua University Intellectual property was carried out in flashover condition (900-1000℃) according to NFPA standards. Destructive tests reveal that multilayer complex based in Basalt fiber mainly with incorporated with Phase Change Materials offer better thermal insulation to the firefighter for at least4.55minutes in flashover conditions (900-1000℃) until reach the second degree of skin burn (44℃). Differential Scanning Calorimeter and Thermogravimetric Analysis show that the best candidates for thermal insulation materials at this temperature due to the heat storage material are Dulcitol and D-Mannitol. The Air Permeability test to optimize the number of thermal batting layers also was studied, and it was found no linear relationship between number of layers and air permeability, and the optimal number was two thermal batting, for the balance of thermal insulation and heat stress.As a conclusion it said the multilayer complex based in the basalt fiber incorporated with phase change materials significant improvement was observed for the thermal insulation for firefighters, in front of the flashover environment, the PCMs has a key role in the insulation to keep the temperature constant in the sample.