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Thermal protective clothing can effectively reduce the damage to personnel in high-tem-perature environments,while a lightweight and efficient insulation layer can minimize the restriction of personnel mobility. In order to obtain structurally superior thermal protective materials, a confined sol-gel strategy was designed to fill poly (p-phenylene benzodioxole) (PBO) nanofibers with sol-gel into flame-retardant viscose/aramid spunlace nonwoven fabric (VAF-NMs). The PBO nanofibers formed a high porosity nanofiber network in the VAF-NMs,and the PBO/VAF-NMs hierarchical micro-nanofiber network mats (TNMMs) were prepared. TNNMs were characterized by transient planar heat source method and thermal protection performance meter, and their thermal conductivity and thermal protection values are 0. 032 W/mK and 35. 2 cal/cm², respectively, showing excellent thermal insulation and thermal protection performance. Through the ultimate oxygen index meter and wearing comfort test,the limit oxygen index of TNNMs is more than 32,the water vapor transmission rate is 2 067 g/(m² • d), and the air permeability is 103 mm/s, which shows excellent flame retardancy and wearing comfort. The strong mechanical properties and stable structure of TNNMs provide new ideas for the design of civilian and industrial thermal protection materials. [ABSTRACT FROM AUTHOR]