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Polybenzoxazine/Melamine (PBa/MS) double network aerogels were prepared using melamine foam (MS) as the backbone and bisphenol A-type benzoxazine (Ba) as the maxtrix. The effect of Ba concentration in the sol-gel on the performance of the double network aerogel was investigated. During the combustion, the PBa/MS composite aerogel exhibited self-extinguishing performance. Compared with PBa-18%, the contact angle of PBa-18%/MS composite aerogel was 18° higher, and the heat release peak (PHRR) and total smoke production (TSP) of the composite aerogel decreased by 7% and 39%, respectively. These values indicate that MS can significantly reduce the release of heat and smoke from the PBa aerogel, thus improving its flame retardancy. In addition, the composite aerogel formed a denser and more complete carbon layer during combustion, which blocks both heat and mass transfer. Thus, the resulting PBa/MS dual-network composite aerogels obtained in the current work are expected to meet the demands for flame-retardant, hydrophobic thermal insulation materials in many fields. [Display omitted] • Benzoxazine/melamine composite aerogel has a double network structure. • Aerogels was prepared through drying at normal temperature and pressure. • Aerogel owned the properties of flame retardancy, smoke suppression, resilience, heat insulation and hydrophobic properties. • The composite aerogel has good thermal insulation at 200 ℃. [ABSTRACT FROM AUTHOR]